LUMINESCENT LANTHANIDE (III)-CHELATED DENDRITIC COMPLEXES HAVING LIGHT-HARVESTING EFFECT AND THEIR SYNTHETIC METHODS Technical Field The present invention relates to new organic luminescent complex compounds containing rare earth metal ions and having a structure represented by a general formula shown below, as well as methods for preparing them. The inventive complex compounds have an increased solubility in polymer medium through the design of their molecular structure so that they are effectively doped in the polymer medium. Also, the inventive compounds are used as planar waveguide-type optical amplifier materials that are new organic luminescent materials, of which photophysical properties are maximized by the processes of absorbing and transferring artificial light using the principle of naturally occurring photosynthetic antenna complexes which show a light- harvesting effect by absorbing photon energy (or light) and transferring the absorbed energy to the central system of the complexes. Moreover, the inventive compounds have a structure where the rare earth metal ions are efficiently encapsulated with organic ligand derivatives.

Background Art The present invention relates to new planar waveguide-type optical amplifier materials having improved solubility and energy transfer capacity. Such materials compensate for light intensity reduction that is a fundamental problem with polymer materials for optical information processing.

The doping concentration of Er+3 in the existing silica

optical fiber is about 100-1,000 ppm. If the doping concentration exceeds this limit, a non-light-emitting process will occur due to the interaction between the Er+3 ions, to cause a rapid reduction in optical amplification efficiency. For this reason, by the method of doping the silica optical fiber with Er+3, it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide-type optical integrated circuits. As new materials to solve this problem and to embody planar waveguide-type optical amplifier devices, polymer materials doped with rare earth metal ions are being noticed. Currently, in industrially advanced nations including Japan, USA and Europe, researches on the development of a planar waveguide-type optical amplifier material comprising a polymer medium doped with a complex compound containing rare earth ions are being conducted.

An optical fiber amplifier device prepared by doping a medium for a PMMA-based polymer optical fiber's core with an organic dye at a doping concentration of about 1 ppm was first reported by Japan Keio University in 1993. This optical device had a relatively large length of 50 cm and showed a very excellent optical amplification property of about 30 dB. However, its optical amplification time is short due to its light- emitting process caused by spontaneous light emission, so that it cannot be used as the planar waveguide-type optical amplifier device. In an attempt to. overcome this problem, this research team reported a polymer device for optical amplification prepared by doping a PMMA-based polymer optical fiber with a rare earth metal having an amplification effect.

Recently, a Kuzyk's research team in USA Texas-Austin University reported an optical amplifier device having a very

short length of 2.2 cm, which had been prepared by doping photolime gel, a water-soluble polymer, with Nd+3, by a spin coating method. This optical amplifier device had an amplification wavelength of 1.06 pm and an amplification gain of 8.5 dB. Also, Dutch Philips Company developed a polymer optical fiber-type optical amplifier device having a very short length of about 1.5 cm, which had been prepared by filling a Teflon capillary tube with a lauryl methacrylate monomer (MA series), doping the monomer with Eu+3, and then polymerizing the doped monomer. This amplifier device was reported to have an amplification gain of 4.1 dB.

Recently, in many research institutes, including a Japan's NTT's photonic research team, several USA universities (Colorado University and Arizona University) and research institutes (Bellcore and Corning) and Canada McGill University, researches on optical amplifier materials prepared by uniformly introducing rare earth metals into an inorganic polymer material (SiO2) by low-temperature sol-gel chemistry are being actively conducted.

Particularly, in 1996, the development of a planar waveguide- type optical amplifier device and an optical amplifier device integrated with WDM was reported. However, such optical amplifier systems have a problem in that their optical amplification effect is insufficient since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals, and the phase separation between the rare earth ions and the silica occurs.

Disclosure of Invention The present invention has been made to solve the above- mentioned problems occurring in the prior art, and an object of

the present invention is to provide rare earth ion-containing organic ligand complex compounds having a structure represented by a general formula shown below, which are prepared by molecular engineering unlike the prior method of doping a polymer with rare earth ions, show a light-harvesting effect as the principle of natural photosynthesis, have excellent solubility in a polymer medium and have no aggregation and interaction between the rare earth metal ions.

Another object of the present invention is to provide methods for preparing dentritic porphyrin organic ligand complex compounds containing rare earth ions and having a structure represented by a general formula shown below.

Still another object of the present invention is to provide compounds showing an optical amplification effect and having a structure represented by a general formula shown below.

Still another object of the present invention is to provide organic ligand complex compounds whose photophysical properties can be controlled by a variety of rare earth metals such that they emit light at various wavelengths as shown in FIG. 6, as well as methods for preparing them.

Still another object of the present invention is to provide a blend of a compound having a general formula shown below and a binder, the blend having an optical amplification effect controlling photophysical properties.

To achieve the above objects, the present invention provides complex compounds containing rare earth metal ions and having a structure represented by the following general formula, as well as methods for preparing them: [General Formula] wherein Ln is Yb, Er or Nd ; a is 0,1 or 2;

and Ra is H or F.

Concretely, the compounds of the general formula are represented by the following chemical formulas (1)- (17) : [Chemical Formula 1] [Chemical Formula 2]

R Ra R Ra a Ra /, ; ' O Ra Ra Ra Ra Ra ra L Ra Ra-j i-J [Chemical Formula 3]. 0 Ln-+--- (-R x 3 where x= 1 or 2 ; [Chemical Formula 4] o. _. where x=l or 2 ; where x=l or 2 ; where x=l or 2 ; [Chemical Formula 5] R'O A \/C 'Lns*-.. __ _...... R \ >.. 4-R 3 3 where x=l or 2 ; [Chemical Formula 6] N HN NH N RVò : tl", NH N- ill ouzo 3 / I- N N O, O I Nli I H N \ FIN . N hl N N 0 i ' [Chemical Formula 7] riz N, N m N N- N N- i,/ 0 0 lu _- . oxo N N /N w w w I N \ M I N N/I w [Chemical Formula 8]

OR' N han ! I w \ NH N- ZU 0 0 XI o RIO R' /\ OR' R \, / \/ v OR' RIO HN N H N N, OR' OR'RIZ [Chemical Formula 9]' OR' O/ RIO OR' N N- N N- rua OUZO R. O Ln3+ OR. \/\ /O' ;/'O/ /N w w I N \ N-I I-\ N N'MN \ N___M w I N N/I RIO OR'R'O [Chemical Formula 10]

/\ i T N., g""Ln j O ffi < g N N HN I \ 1 i/ 3 [Chemical Formula 11] i'Q \ I N., :,-Ln3+ I I \ 6/ I \ 1 i/ i 3 [Chemical Formula 12] w N,"NH N- N------Ln + 1", 0 N HN '\ 6/, N 3- [Chemical Formula 13]

I r v 4> Ln'9 0 N N N \ [Chemical Formula 14] OR' / Fiv \W N. , : Ln3* /\ NH N-- N' O N HN I I 3 OR' ; [Chemical Formula 15] OR' / fiv \W N., = ; Ln3* I'/\ NeM, DN OR' , N,. 0 I \ 1 i f 3 OR' [Chemical Formula 16] OR' N,"'-Ln NH N-OR ! N han /N, ; \ 1 i f N N OR'and OR' ; and [Chemical Formula 17] OR' s N, l N, N /N_____ ; Ln3* /\ \ NMN R, 0 N''N \ / 3 3 OR'

Brief Description of Drawings FIG. 1 shows the comparison of photoluminescence intensity between metal complexes; FIG. 2 shows the photoluminescence intensity of a complex compound substituted with dendron; FIG. 3 shows the effect of dendron in naphthalene; FIG. 4 shows the photoluminescence effect of naphthalene- dendron; FIG. 5 shows the comparison between Yb3+-(Pt-por l) (terpy) and Yb3+-(G2-Pt-por 1) 3 (terpy); and FIG. 6 shows changes in photoluminescence wavelength and

photoluminescence intensity with rare earth metals.

Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail by examples for the synthesis of intermediates and examples for the preparation of rare earth ion-containing luminescent complex compounds. However, it will be obvious to a person skilled in the art that the present invention is not limited to or by the examples.

In the examples, the following substances were used to prepare the compounds of the present invention: KH (dispersion in mineral oil), pyrrole, benzaldehyde, 4-hydroxybenzaldehyde, trifluoroacetic acid (TFA), BF3-OEt2, 2, 2'-dipyridyl, and 2, 2' : 6', 2"-terphyridine, which are commercially available from Aldrich Co. ; pentafluorobenzoic acid which is commercially available from TCI Co. ; methyl-4-formylbenzoate which is commercially available from Fluka Co. ; 2,3-dichloro-5, 6-dicyano- 1,4-benzoquinone (DDQ) which is commercially available from Acros Co.; benzoic acid which is commercially available from Janssen Co.; anhydrous ErCl3 which is commercially available from Stem Co. ; anhydrous YbCl3 and anhydrous NdCl3 which are commercially available from Aldrich Co.; absolute ethanol and methanol which are commercially available from J. T. Baker Co. ; and THF, hexane, toluene, chlorobenzene, dichloromethane, ethanol, acetone, HC1, KOH, and MgSO4 which are commercially available from Sam Jun Chemical Co. Of such substances, THF, hexane and toluene were used immediately after purification in the presence of Na/benzophenone, and CHC13 and CH2Cl2 were used immediately after purification in the presence of CaH2 and P205.

The other substances were used without separate purification.

The structure of compounds prepared in the examples was analyzed by 1H-NMR, 13 C-NMR and FT-IR spectrometric methods. The H-NMR results were recorded using a Varian 300 spectrometer, and all chemical shifts were recorded in ppm units per tetramethyl silane as the internal standard. IR spectra were measured on KBr pellets using a Perkin-Elmer spectrometer. Luminescent spectra were measured in a solid state by FS920 (Edinburgh Instruments Ltd.) Hereinafter, examples for the synthesis of intermediates, examples for the preparation of complex compounds of the present invention, and examples for the preparation of a blend consisting of the compound prepared in the preparation examples and a polymer substance, such as fluorinated or non-fluorinated polystyrene, polyimide, polymethylmethacrylate, polyamide, polyether or polyester, and the photoluminescence efficiency of the blend, will be described. However, it will be obvious to a person skilled in the art that the present invention is not limited by or to the examples.

Synthesis of Intermediates Synthetic'Example 1: Preparation of 5-Phenyldipyrromethane (Reaction Scheme 1) 31.61 g (471.16 mmol) of pyrrole and 10 g (94.23 mmol) were introduced into a round-bottom flask, and stirred for 5 minutes at room temperature. The stirred material was added with 726 Ll (9. 42 mmol) of trifluoroacetic acid (TEA) and stirred for 5 minutes at room temperature, after which 25 ml of 0. 1N NaOH aqueous solution was introduced into the reactor to terminate the reaction. After the reaction mixture was extracted with dichloromethane, the organic solvent and the pyrrole were completely evaporated. The remaining material was distilled in vacuum using a Kugelrohr apparatus to give a yellow compound.

The yellow compound obtained by the distillation was dissolved in ethanol and recrytallized by the addition of a small amount of water to give a white crystal.

IH NMR (CDC13, ppm) : 5.47 (s, 1H, meso-H), 5.91 (m, 2H, pyrrole- H), 6.15 (q, 2H, pyrrole-H), 6.69 (q, 2H, pyrrole-H), 7.19-7. 35 (m, 5H, Ar-H), 7.89 (br s, 2H, NH) [Reaction Scheme 1] TFA (0. 1 Q pyrrole (5 eq.) CHO R. T., 5 min NU HO

Synthetic Example 2 : Preparation of 5- (4- methoxycarbonylphenyl) dipyrromethane (Reaction Scheme2) The title compound was prepared under the same conditions as in Synthetic Example 1 except that 4-methyl 4-formylbenzoate was used instead of benzaldehyde.

1H NMR (CDC13, ppm) : 3.90 (s, 3H, CH3), 5.47 (s, 1H, meso- H), 5.89 (m, 2H, pyrrole-H), 6.16 (q, 2H, pyrrole-H), 6.71 (q, 2H, pyrrole-H), 7.96 (m, 4H, Ar-H and NH)' [Reaction Scheme 2] COOCH3 COACH3 TFA (0. 1 eq.) N pyrrole (5 eq.) CHO R. T., 5 min NH HN

Synthetic Example 3: Preparation of (5,10, 15-triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction Scheme3) 1.76g (7. 92mmol) of phenyldipyrromethane, 2.22 g (7.92 mmol) of (5- (4-methoxy-carbonylphenyl) dipyrromethane, 1.68 g (1.84 mmol) of benzaldehyde and 792 mL (~10-2 M) of CHC13 were introduced into a reaction flask and stirred for 10 minutes at

room temperature. The stirred mixture was added with 502 pL (3.96 mmol) of BF3OEt2 and stirred for 30 minutes at room temperature, and then, added with 5.39 g (23.76 mmol) of DDQ and stirred for one hour. The resulting solution was distilled under reduced pressure to remove the solvent. The remaining material was separated by column chromatography (silica, CHCL3) and then washed with cold ethanol to give the title compound.

1H NMR (CDC13, ppm) : 5 8.95-8. 97 (d, 6H, ß-pyrrole), 8.88- 8. 89 (d, 2H, ß-pyrrole) 8,. 52-8.55 (d, 2H, Ar-H), 8. 39-8.42 (d, 2H, Ar-H), 8.31-8. 33 (m, 6H, Ar-H), 7. 83-7. 84 (m, 9H, Ar-H), 4.11 (s, 3H,-OCH3),-2. 68 (s, 2H, NH) [Reaction Scheme 3] Synthetic Example 4 :, Preparation of ( [5, 10,15-Triphenyl-20- (4-methoxycarbonylphenyl) pcrphyrin] zinc (Reaction Scheme 4) 0. 88 g (1.31 mol) of 5,10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porph'yrin, 1.44 g (6.55 mmol) of zinc acetate dihydrate and 50 ml of THF 50 were introduced into a reaction flask and stirred'at reflux overnight. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted witlz CHC13, and washed several times with aqueous sodium bicarbonate solution and water. The organic layer was dried with anhydrous sodium sulfate and the solvent was removed under reduced pressure. The remaining material was

washed with cold ethanol, and dried under vacuum to give the title compound.

1H NMR (CDC13, ppm) : 6 8. 86 (s, 6H, (3-pyrrole), 8. 80 (d, 2H, P- pyrrole), 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H, Ar-H), 7.77 (m, 9H, Ar-H), 4.11 (s, 3H,-OCH3) [Reaction Scheme 4] Synthetic Example 5: Preparation of ( [5, 10,15-Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 5) 0.311 g (0.462 mmol) of 5,10, 15-tripheny-20- (4- methoxycarbonylphenyl) porphyrin, 0.246 g (0.924 mmol) of platinum (II) chloride and 25 ml of benzonitrile were introduced into a reaction flask, and stirred at reflux for 30 hours. After completion of the reaction, the reaction mixture was cooled to room temperature. After the cooled material was diluted with CH2C12, the solvent was completely removed under reduced pressure.

The remaining material was separated by column chromatography (silica, MC) to give the title compound.

1H NMR (CDC13, ppm) : 5 8. 76 (s, 6H, P-pyrrole), 8.69 (d, 2H, ß- pyrrole), 8.50 (d, 2H, Ar-H), 8.30 (d, 2H, Ar-H), 8.27 (d, 6H, Ar-H), 7.75 (m, 9H, Ar-H), 4.11 (s, 3H,-OCH3) [Reaction Scheme 5] \ \ I/I/ 1' Y Y i i NH N Benzonitrile-N'\N 9 Reflux < COOCH3 COOCH3

Synthetic Example 6: Preparation of (5,10, 15-Triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 6) 0.94 g (1.39 mmol) of 5,10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin, 0.78 g (13.97 mmol) of KOH, THF- ethanol (1: 1), and distilled water were introduced into a reaction flask and stirred at reflux overnight. After completion of the reaction, the reaction solution was cooled to room temperature and adjusted to a pH of 2 by the addition of concentrated hydrochloric acid. This was extracted with CHC13, and the organic layer was washed several times with aqueous sodium bicarbonate solution and water, and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (Silica ; CHC13 : MeOH = 9 : 1). The product was washed with cold ethanol and dried under vacuum to give the title compound.

1H NMR (CDC13, ppm) : 5 8.86 (s, 6H, (3-pyrrole), 8.80 (d, 2H, (3- pyrrole), 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H, Ar-H), 7.77 (m, 9H, Ar-H), -2. 65 (s, 2H, NH) [Reaction Scheme 6] I I Y Y Y \-N HN -KOH -N HN NH HNX THF I EtOH XN HN X \ e Reflux \ / ye v COOCH3 COOH

Synthetic Example 7: Preparation of ( [5, 10,15-triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 7) The title compound was prepared in the same manner as in Example 6 except that [5,10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc was used instead of 5,10, 15-triphenyl-20- (4-methoxycarbonylphenyl) porphyrin.

1H NMR (CDC13, ppm) : 5 8. 86 (s, 6H, P-pyrrole), 8. 80 (d, 2H, (3- pyrrole), 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H, Ar-H), 7.77 (m, 9H, Ar-H) [Reaction Scheme 7] I I -N, N-N N oh /\ N Zn N \/THF/EfOH/\ N Z N \/ I, Reflux I' I I COOCH3 COOH Synthetic Example 8: Preparation of ( [5, 10,15-triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 8) The title compound was prepared in the same manner as in Example 6 except that [5,10, 15-triphenyl-20- (4-

methoxycarbonylphenyl) porphyrin] platinum was used instead of 5,10, 15-triphenyl-20- (4-methoxycarbonylphenyl) porphyrin.

1H NMR (CDC13, ppm) : 5 8. 76 (s, 6H, (3-pyrrole), 8. 69 (d, 2H, P-pyrrole), 8.50 (d, 2H, Ar-H), 8.30 (d, 2H, Ar-H), 8.27 (d, 6H, Ar-H), 7.75 (m, 9H, Ar-H) [Reaction Scheme 8] i i w 1' oY _N,. N KOH-N, N/ N N THF I ETOH N N reflux \ v v COOCH3 COOH Synthetic Example 9 : Preparation of (5- (4- hydroxyphenyl) dipyrromethane (Reaction Scheme 9) 27.47 g (409.43 mmol) of pyrrole and 10 g (81.88 mmol) of 4-hydroxybenzaldehyde were introduced into a round-bottom flask and stirred for 5 minutes at room temperature. The solution was added with 630.85 ul (8.19 mmol) of trifluoroacetic acid (TFA), and stirred for 5 minutes at room temperature.'25 ml of 0. 1N NaOH aqueous solution was introduced into the reactor to terminate the reaction. After the resulting solution was extracted with dichloromethane, the organic solvent and the pyrrole were completely evaporated. -The remaining material was separated by column chromatography (silica; MC/EA=4: 1) to give the title compound.

H NMR (CDC13, ppm) : 5.25 (s, 1H, meso-H), 5. 91 (s, 1H, OH), 6'. 17 (m, 2H, pyrrole-H), 6.67 (m, 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.94 (br s, 2H, NH) [Reaction Scheme 9] OH OH \ S 3 TFA (01 eq) 4 'pyrrole (5 e. CHO PY CHO H R. T., 5 min

Synthetic Example 10: Preparation of [G-l]-aldehyde (Reaction Scheme 10) 0. 3 g (2.45 mmol) of 4-hydroxybenzaldehyde, 1.98 g (2.45 mmol) of [G-l]-Br, 1.70 g (12.28 mmol) of K2CO3, 100 ml of acetone and a small amount of water were introduced into a reaction flask and stirred at reflux for 24 hours. After completion of the reaction, the solution was cooled to room temperature, and the solvent was removed under reduced pressure.

The remaining material was extracted with MC and dried with anhydrous'MgS04. After the solvent was removed under reduced pressure, the residue was separated by column chromatography (silica ; MC) to give the title compound.

1H NMR (CDC13, ppm) : 5.04 (s, 4H), 5.08 (s, 2H), 6.52 (t, 1H), 6. 66 (d, 2H), 7.04 (d, 2H), 7.40-7. 35 (m, 10H), 7.82 (d, 2H), 9. 88 (s, 1H) Synthetic Example 11: Preparation of [G-2]-aldehyde (Reaction Scheme 10) The title compound was prepared in the same manner as in Synthetic Example 10 except that [G-2] -Br was used instead of [G-l]-Br.

1H NMR (CDC13, ppm) : 4.92 (s, 4H), 4.97 (s^, 8H), 4. 99 (s, 2H), 6. 54. (t, 1H), 6.62 (d, 2H), 6.65 (d, 4H), 7.04 (d, 2H), 7.20- 7. 38 (m, 20H), 7. 76 (d, 2H), 9.79 (s, 1H)

Synthetic Example 12: Preparation of [G-3]-aldehyde (Reaction Scheme 10) The title compound was prepared in the same manner as in Synthetic Example 10 except that [G-3] -Br was used instead of [G-l]-Br.

1H NMR (CDC13, ppm) : 4.95 (s, 24H), 4.98 (s, 4H), 5.16 (s, 2H), 6.52 (t, 4H), 6.55 (t, 2H), 6.62 (t, 1H), 6.65 (d, 8H), 6.71 (d, 4H), 6.87 (d, 2H), 7.21-7. 38 (m, 42H), 8.08 (d, 2H), 9.80 (s, 1H) Synthetic Example 13: Preparation of [G-4]-aldehyde (Reaction Scheme 10) The title compound was prepared in the same manner as in Synthetic Example 10 except that [G-4] -Br was used instead of [G-l]-Br.

1H NMR (CDC13, ppm) : 4.75-4. 69 (s, 56H), 4.91 (s, 4H), 5.06 (s, 2H), 6. 48 (t, 8H), 6. 52 (t, 4H), 6.55 (t, 2H), 6. 60 (t, 1H), 6.62 (d, 16H), 6.65 (d, 8H), 6.71 (d, 4H), 6.87 (d, 2H), 7.21- 7.38 (m, 82H), 7.98 (d, 2H), 9.82 (s, 1H) [Reaction Scheme 10] OH O, [Gn] K c + [Gn]-Br- Acetone/water reflue CHO CHO n\ 0 [Gn] zozo '° v i (Gn] ; 1.,, \/ p I w O (G-1) (G-2)

Synthetic Example 14: Preparation of [G-1]-5- (4- hydroxyphenyl) dipyrromethane (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 10 except that 5- (4- hydroxyphenyl) dipyrromethane was used instead of 4- hydroxybenzaldehyde.

1H NMR (CDC13, ppm) : 5.04 (s, 4H), 5.08 (s, 2H), 5.25 (s, 1H, meso-H), 6.17 (m, 2H, pyrrole-H), 6.52 (t, 1H), 6.66 (d, 2H), 6.67 (m, 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.40-7. 35 (m, 10H), 7.94 (br s, 2H, NH) Synthetic Example 15: Preparation of ( [G-2]-5- (4- hydroxyphenyl) dipyrromethane (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-2] -Br was used instead of [G-l]-Br.

H NMR (CDC13, ppm) : 4.92 (s, 4H), 4.97 (s, 8H), 4.99 (s, 2H), 5.25 (s, 1H, meso-H), 6.17 (m, 2H, pyrrole-H), 6.54 (t, 1H), 6.62 (d, 2H), 6.65 (d, 2H), 6.67 (m, 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.20-7. 38 (m, 20H), 7.94 (br s, 2H, NH) Synthetic Example 16: Preparation of ( [G-3]-5- (4- hydroxyphenyl) dipyrromethane) (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-3] -Br was used instead of [G-l]-Br.

1H NMR (CDC13, ppm) : 4.95 (s, 24H), 4. 98 (s, 4H), 5. 16 (s, 2H), 5.25 (s, 1H, meso-H), 6.17 (m, 2H, pyrrole-H), 6.52 (t, 4H), 6. 55 (t, 2H), 6.62 (t, 1H), 6.65 (d, 8H), 6.67 (m, 2H, pyrrole- H), 6.71 (d, 4H), 6.73 (d, 2H, Ar-H), 6.87 (d, 2H), 7.06 (d, 2H, Ar-H), 7.20-7. 38 (m, 42H), 8.80 (d, 2H), 7.94 (br s, 2H, NH) Synthetic Example 17: Preparation of ( [G-4]-5- (4- hydroxyphenyl) dipyrromethane) (Reaction Scheme 11)

The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-4]-Br was used instead of [G-l]-Br.

1H NMR (CDC13, ppm) : 4. 75-4. 69 (s, 56H), 4.91 (s, 4H), 5.06 (s, 2H), 5.25 (s, 1H, meso-H), 6. 17 (m, 2H, pyrrole-H), 6.48 (t, 8H), 6.52 (t, 4H), 6.55 (t, 2H), 6.60 (t, 1H), 6.62 (d, 16H), 6.65 (d, 8H), 6.67 (m, 2H, pyrrole-H), 6.71 (d, 4H), 6.73 (d, 2H, Ar-H), 6.87 (d, 2H), 7.06 (d, 2H, Ar-H), 7.21-7. 38 (m, 82H), 7.98 (d, 2H), 7.94 (br s, 2H, NH) [Reaction Scheme 11] OH 0 [Gn] i t K2CO3 h + [Gn]-Br- Acetone/water refs lux CNH HN/ gNH HNsY %, NH HN@> Synthetic Example 18: Preparation of ([G-1] 3-5, 10,15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction Scheme 12) The title compound was prepared in the same manner as in Synthetic Example 3, using [G-1]-5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-l]-benzaldehyde.

H NMR (CDC13, ppm) : # -2. 68 (s, 2H), 4.11 (s, 3H), 5.11 (s, 12H), 5. 23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46. (m, 36H), 8.31 (m, 6H), 8.39 (d, 2H), 8. 52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 19: Preparation of ( [G-213-5, 10,15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction Scheme 12)

The title compound was prepared in the same manner as in Synthetic Example 3, using [G-2]-5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-l]-benzaldehyde.

1H NMR (CDC13, ppm) : õ-2. 69 (s, 2H), 4.12 (s, 3H), 5.03 (s, 24H), 5.05 (s, 12H), 5.25 (s, 6H), 6.58 (t, 6H), 6-. 63 (t, 3H), 6.73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8. 39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8. 88 (d, 2H) Synthetic Example 20 : Preparation of ([G-3] 3-5, 10,15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction Scheme 12) The title compound was prepared in the same manner as in Synthetic Example 3, using [G-3]-5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-3]-benzaldehyde.

1H NMR (CDC13, ppm) : õ-2. 72 (s, 2H), 4.12 (s, 3H), 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7 ; 21- 7. 38 (m, 126H), 8. 08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 21: Preparation of ([G-4] 3-5, 10,15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reactoion Scheme 12) The title compound was prepared in the same manner as in Synthetic Example 3, using [G-4]-5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-4]-benzaldehyde.

. IH NMR (CDC13, ppm) : 5-2. 72 (s, 2H), 4.12 (s, 3H), 4.75-4. 69 (s, 168H), 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6. 62 (t, 3H), 6.62 (d, 48H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d,. 6H), 8. 88 (d, 2H) [Reaction Scheme 12]

Synthetic Example 22: Preparation of (EG-113- [5, 10,15- Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13) The title compound was prepared in the same manner as in Synthetic Example 4, using [G-1] 3-5,10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin.

H NMR (CDC13, ppm) : 5 4. 11 (s, 3H), 5.11 (s, 12H), 5. 23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46 (m, 36H), 8.31 (m, 6H), 8.39 (d, 2H),'8. 52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 23: Preparation of ([G-2]3-[5, 10,15- Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13) The title compound was prepared in the same manner as in Synthetic Example 4, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin. (Compounds which contain G-3 and G-4, respectively, were prepared in the same manner, using G-3 and G-4).

H NMR (CDC13, ppm) : # 4.12 (s, 3H), 5.03 (s, 24H), 5.05 (s, 12H), 5.25 (s, 6H), 6. 58 (t, 6H), 6.63 (t, 3H), 6.73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H)

Synthetic Example 24: Preparation of ( [G-3] 3- [5, 10,15- Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13) The title compound was prepared in the same manner as in Synthetic Example 4, using [G-3] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin.

1H NMR (CDC13, ppm) : 5 4.12 (s, 3H), 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.21-7. 38 (m, 126H), 8. 08 (m, 6H), 8. 39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 25: Preparation of ( [G-4] 3- [5, 10,15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13) The title compound was prepared in the same manner as in Synthetic Example 4, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin.

H NMR (CDC13, ppm).. 4.12 (s, 3H), 4.75-4. 69 (s, 168H), 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.62 (d, 48H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) [Reaction Scheme]

Synthetic Example 26: Preparation of ( [G-1] 3- [5, 10,15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14) The title compound was prepared in the same manner as in Synthetic Example 5, using [G-1] 3-5,10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.

H NMR (CDC13, ppm) : 5 4.11 (s, 3H), 5.11 (s, 12H), 5.23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46 (m, 36H), 8.31 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 27: Preparation of ([G-2]3-[5, 10,15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14) The title compound was prepared in the same manner as in Synthetic Example 5, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.

IH NMR (CDC13, ppm) : 5 4.12 (s, 3H), 5.03 (s, 2. 4H), 5.05 (s, 12H), 5.25 (s, 6H), 6.58 (t, 6H), 6.63 (t, 3H), 6. 73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 28: Preparation of ( [G-3] 3- [5,10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14).

The title compound was prepared in the same manner as in Synthetic Example 5, using [G-3] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.

H NMR (CDC13, ppm) : 5 4.12 (s, 3H), 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.21-7. 38 (m, 126H),

8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8. 88 (d, 2H) Synthetic Example 29: Preparation of ( [G-4] 3- [5, 10,15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14) The title compound was prepared in the same manner as in Synthetic Example 5, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.

H NMR (CDC13, ppm) : 5 4.12 (s, 3H), 4.75-4. 69 (s, 168H), 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.62 (d, 48H), 6. 65 (d, 24H), 6.71 (d, 12H), 6. 87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) [Reaction Scheme 14] IGnl. O 1 1 in 1 11 b 0"0 pi 0 NH N- N N^ --i I I i i C02CH3 COACH3 . Synthetic Example 30: Preparation of ([G-1] 3-5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-1] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin.

H NMR (CDC13, ppm) : 5-2. 68 (s, 2H), 5.11 (s, 12H), 5.23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46 (m, 36H), 8.31 (m, 6H), 8. 39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H)

Synthetic Example 31 : Preparation of ([G-2]3-5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin.

1H NMR (CDC13, ppm) : 6-2. 69 (s, 2H), 5.03 (s, 24H), 5.05 (s, 12H),'5. 25 (s, 6H), 6.58 (t, 6H), 6.63 (t, 3H), 6.73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 32: Preparation of ( [G-3] 3-5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-3] 3-5, 10, 15-triphenyl-20- (4-methoxycarbonyl) porphyrin.

1H NMR (CDC13, ppm) : 5-2. 72 (s, 2H), 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.21-7. 38 (m, 126H), 8. 08 (m, 6H), 8. 39 (d, 2H), 8.52 (d, 2H), 8. 95 (d, 6H), 8. 88 (d, 2H) Synthetic Example 33: Preparation of ([G-4]3-5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin.

H NMR (CDC13, ppm) : 5-2. 72 (s, 2H), 4.75-4. 69 (s, 168H), 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.62 (d, 48H), 6.65 (d, 24H), 6.71 (d, 12H), 6. 87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) [Reaction Scheme 15] LGnlO 1 1 / \/ \ /. \/N NH \/O [Gnl KOH [Gn] O \ N N \/ NH N-THF I ETOH I HO NH N- reflux COACH3 COOH

Synthetic Example 34: Preparation of ( [G-l] 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16) The title compound was prepared in the same as in Synthetic Example 6, using [G-1] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.

'H NMR (CDC13, ppm) : 5 5.11 (s, 12H), 5.23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46 (m, 36H), 8.31 (m, 6H), 8.39 (d, 2H), 8. 52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 35: Preparation of ([G-2]3-[5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16) The title compound was prepared in the same as in Synthetic Example 6, using [G-2]3-[5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.

H NMR (CDC13, ppm) : # 5.03 (s, 24H), 5. 05 (s, 12H), 5.25 (s, 6H), 6.58 (t, 6H), 6.63 (t, 3H), 6.73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 36: Preparation of ( [G-3] 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16)

The title compound was prepared in the same as in Synthetic Example 6, using [G-3] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.

H NMR (CDC13, ppm) : 5 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.21-7. 38 (m, 126H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8. 88 (d, 2H) Synthetic Example 37: Preparation of ([G-4]3-[5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16) The title compound was prepared in the same as in Synthetic Example 6, using [G-4] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.

1H NMR (CDCl3, ppm) : 6 4. 75-4.69 (s, 168H), 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.62 (d, 48H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) [Reaction Scheme 16] 0 [Gn] O, [Gn] I I i i [Gn] N-, [Gn] KOH In10/\ Nz'n _ O IGn] N N-THF I ETOH I H20 N- reflux C02CH3 COOH Synthetic Example 38: Preparation of ( [G-11 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 17)

The title compound was prepared in the same manner as in Synthetic Example 6, using [G-1] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.

1H NMR (CDC13, ppm) : 5 5.11 (s, 12H), 5. 23 (s, 6H), 6.68 (t, 3H), 6.87 (d, 6H), 7.30-7. 46 (m, 36H), 8.31 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 39: Preparation of ( [G-2] 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 17) The title compound was prepared in the same manner as in Synthetic Example 6, using [G-2] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.

1H NMR (CDC13, ppm) : 5 5.03 (s, 24H), 5.05 (s, 12H), 5.25 (s, 6H), 6.58 (t, 6H), 6. 63 (t, 3H), 6.73 (d, 12H), 6.86 (d, 6H), 7.23-7. 40 (m, 66H), 8.10 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) Synthetic Example 40: Preparation of ( [G-3] 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 17) The title compound was prepared in the same manner as in Synthetic Example 6, using [G-3] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.

1H NMR (CDC13, ppm) : 5 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.65 (d, 24H), 6.71 (d, 12H), 6.87 (d, 6H), 7.21-7. 38 (m, 126H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H)

Synthetic Example 41: Preparation of ( [G-4] 3- [5, 10,15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 17) The title compound was prepared in the same manner as in Synthetic Example 6, using [G-4] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.

1H NMR (CDC13, ppm) : 5 4.75-4. 69 (s, 168H), 4.91 (s, 12H), 5. 06 (s, 6H), 6.48 (t, 24H), 6.52 (t, 12H), 6.55 (t, 6H), 6.62 (t, 3H), 6.62 (d, 48H), 6. 65 (d, 24H), 6.71 (d, 12H), 6. 87 (d, 6H), 7.19-7. 38 (m, 252H), 8.08 (m, 6H), 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, 6H), 8.88 (d, 2H) [Reaction Scheme 17] I I RIZ RIZ N., P. N O IGnI KOH Gn /\ N'Pt N -O IGn] __ _ 0-N.'Of. N-THF I ETOH I H20-li'N- reflux I I j reftux ' C02CH3 COOH Synthetic. Example 42: Preparation of 1- (4-carboxyphenyl)- naphthalene (Reaction Scheme 18) 1.00 g (4.58 mmol) of 1- (4-methylphenyl)-naphthalene [NA-1] and 1.16 g (7.33 mmol) of potassium permanganate were dissolved in 40. ml of a 7: 3 mixture solution of pyridine and water. The solution was stirred for 24 hours at 120 °C and cooled to room temperature. The by-product MnO2 was filtered out and the crude product was adjusted to pH 1 by the addition of hydrochloric acid. The formed solid was washed several times with water to give l-(4-carboxyphenyl)-naphthalene ([NA-1]-CO2H).

FT-IR (KBr, cm- : 3400-2200 (broad), 1683, 1607,1419, 1293, 1111, 778. 1H NMR (DMSO-d6, ppm) : 8.10 (d, 2H), 8.02 (t, 2H), 7.60 (d, 1H), 7.58-7. 45 (m, 6H). EI-Mass calcd. for C17Hl2O2 : 248. 08. Found: 248 [Reaction Scheme 18]

Synthetic Example 43: Preparation of [1- (4-carboxyphenyl)- 4- (4-methoxyphenyl) naphthalene] (Reaction Scheme 19) The title compound was prepared in the same manner as in Synthetic Example 42 except that 1- (4-methylphenyl)-4- (4- methoxyphenyl) naphthalene [NA-2] was used instead of 1- (4- methylphenyl) -naphthalene [NA-1].

FT-IR (KBr, cm 1). 3300-2200 (very broad), 2928,1682, 1436, 1247,1119, 824, 722. 1H NMR (DMSO-d6, ppm) : 8.16 (d, 2H), 7.. 87 (t, 2H), 7.51-7. 42 (m, 8H), 7.12 (d, 2H), 3.85 (s, 3H) ; EI-Mass calcd. for C24H1803 : 354.13. Found: 354 [Reaction Scheme 19] Synthetic Example 44: Preparation of 9- (4-carbonylphenyl)- 10- (4-methoxyphenyl) anthracene (Reaction Scheme 20) The title compound was prepared in the same manner as in Synthetic Example 42 except that 1- (4-methylphenyl)-4- (4- methoxyphenyl) anthracene [AN-1] was used instead of 1- (4- methylphenyl) -naphthalene [NA-1].

FT-IR (KBr, cm : 3300-2200 (very broad), 2925,1683, 1600, 1508,1238, 1119,825, 724. 1H NMR (DMSO-d6, ppm) : 7.93 (d, 2H), 7. 78 (m, 2H), 7.62 (d, 2H)., 7. 54 (m, 2H), 7. 40-7. 34 (m, 6H), 7.16 (d, 2H), 3.97 (s, 3H) EI-Mass calcd. for C28H2003 : 404.14.

Found: 404 [Reaction Scheme 20] Synthetic Example 45: Preparation of [NA-3] 2-CO2H (Reaction Scheme 21) As shown in Reaction Scheme 21 below, 1. 90 g (2. 34 mmol) of [NA-3] 2-CO2Me and 1.05 g (18.70 mmol) of KOH were dissolved in 26 ml of a 10: 3 mixture solution of ethanol and water. The solution was stirred for 4 hours at 120 °C and then cooled to room temperature. The reaction product was adjusted to pH 1 by the addition of hydrochloric acid. The formed solid was washed several times with water to give [NA-3]2-CO2H.

FT-IR (KBr, cm-1) 3300-2'100 (very broad), 1690,1510, 1250, 1160,830, 760. 1H NMR (DMSO-d6, ppm) : 7.91 (m, 4H), 7.63 (d, 4H), 7. 56-7.42 (m, 16H), 7.27 (d, 2H), 7.12 (d, 2H), 7.07 (t, 1H), 5.30 (s, 4H), 3.85 (s, 6H). EI-Mass calcd. for C55H4206 : 798.30. Found: 798.

[Reaction Scheme 21]

Synthetic Example 46: Preparation of [AN-2] 2-CO2H (Reaction Scheme 22) As shown in Reaction Scheme 22 below, [AN-2]2-CO2H was prepared in Synthetic Example 45 except that [AN-2] 2-CO2Me was used instead of [NA-3]2-CO2Me.

FT-IR (KBr, cm- : 3300,1690 (vC=O), 1246 (vc-o). 1H NMR (DMSO-d6, ppm) : 8.05 (m, 4H), 7.53-7. 45 (m, 26H), 7.12 (d, 4H), 7.03 (m, 1H), 5.22 (s, 4H), 3.91 (s, 6H) [Reaction Scheme 22] Synthetic Example 47: Preparation of [G-1]-[NA-2]-CO2H (Reaction Scheme 23) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-1]- [NA-2] was used instead of [NA-1].

FT-IR (KBr, cari) : 3300-2200 (very broad), 3028, 2922,1692, 1595, 1448,1166, 1030, 741. 1H NMR (CDC13, ppm) : 8.10 (m, 1H), 7.81 (m, 2H), 7.66 (m, 2H), 7.48-7. 33 (m, 17H), 7.12 (d, 2H), 6.87 (d, 2H), 6.68 (t, 1H), 5.10 (s, 2H), 5.04 (s, 4H) ; EI-Mass calcd. for C44H3405 : 642.24. Found: 642 [Reaction Scheme 23]

Synthetic Example 48: Preparation of [G-2]-[NA-2]-CO2H (Reaction Scheme 24) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-2]- [NA-2] was used instead of [NA-1].

FT-IR (KBr, cm 1). 3300-2200 (very broad), 3032,2920, 1692, 1596,1448, 1162, 1030, 7'40. 1H NMR (CDC13, ppm) : 8. 14 (m, 1H), 7.82 (m, 2H), 7.66 (m, 2H), 7.48-7. 31 (m, 27H), 7.12 (d, 2H), 6.74 (d, 2H), 6.70 (d, 4H), 6.58 (t, 3H), 5.09 (s, 2H), 5.04 (s, 8H), 5.00 (s, 4H); FAB-Mass calcd. for C72H5809 : 1066.41. Found: 1066 [Reaction Scheme 24] Synthetic Example 49: Preparation of [G-3]-[NA-2]-CO2H (Reaction Scheme 25) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-3]- [NA-2] was used instead of [NA-1].'

FT-IR (KBr, cm : 3300-2200 (very broad), 3032,2920, 1692, 1596, 1448, 1162,1030, 742. 1H NMR (CDC13, ppm) : 8.14 (m, 1H), 7.82 (m, 2H), 7.65 (m, 2H), 7.52-7. 31 (m, 47H), 7.12 (d, 2H), 6.85 (d, 4H), 6.78 (d, 8H), 6.74 (m, 6H), 6.62 (t, 3H), 5.07 (s, 2H), 5.02 (s, 16H), 4.96 (s, 12H); FAB-Mass calcd. for C128H106O17 : 1914.74. Found: 1914 [Reaction Scheme 25] Synthetic Example 50: Preparation of [G-4]-[NA-2]-CO2H (Reaction Scheme 26) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-4]- [NA-2] was used instead of [NA-1].

FT-IR (KBr, cari) : 3300-2200 (very broad), 3028,2925, 1693, 1593,1452, 1165,1031, 740. 1H NMR (CDC13, ppm) : 8.12 (m, 1H), 7.83 (m, 2H), 7.67 (m, 2H), 7.52-7. 31 (m, 87H), 7.11 (d, 2H), 6. 86 (d, 8H), 6. 78 (d, 16H), 6. 76 (m, 18H), 6. 65 (t, 3H), 5. 09 (s, 2H), 5. 04 (s, 32H), 4.97 (s, 28H); FAB-Mass calcd. for C240H202033 : 3611.41. Found: 3611 [Reaction Scheme 26]

Synthetic Example 51: Preparation of [G-1]- [AN-l]-CO2H (Reaction Scheme 27) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-1]- [AN-1] was used instead of [NA-1].

FT-IR (KBr, cm-1) 3300-2200 (very broad), 3025,2920, 1693, 1592,1447, 1162,1032, 742. 1H NMR (CDC13, ppm) : 7.92 (d, 2H), 7.98 (dd, 2H), 7.63 (d, 2H), 7.54 (dd, 2H), 7.48-7. 33 (m, 16H), 7.16 (d, 2H), 6.76 (d, 2H), 6.58 (t, 1H), 5.09 (s, 2H), 5.02 (s, 4H); EI-Mass calcd. for C48H3605 : 692.26. Found: 692 [Reaction Scheme 27] Synthetic Example 52: Preparation of [G-2]-[AN-1]-CO2H (Reaction Scheme 28) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-2]-[AN-1] was used instead of [NA-1].

FT-IR (KBr, cm : 3300-2200 (very broad), 3032,2920, 1692, 1596,1448, 1162,1030, 740. 1H NMR (CDC13, ppm) : 7.92 (d, 2H), 7. 79 (dd, 2H), 7.62 (d, 2H), 7.54 (dd, 2H), 7. 48-7. 32 (m, 26H), 7.16 (d, 2H), 6. 77 (d, 2H), 6.71 (d, 4H), 6.59 (t, 3H), 5. 13 (s, 2H), 5.04 (s, 8H), 5.02 (s, 4H) ; EI-Mass calcd. for C76H6009 : 1116.42. Found: 1116 [Reaction Scheme 28] Synthetic Example 53: Preparation of [G-3]-[AN-1]-CO2H (Reaction Scheme 29) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-3]- [AN-1] was used instead of [NA-1].

FT-IR (KBr, cm 1) : 3300-2200 (very broad), 3032,2920, 1692, 1596,1448, 1162,1030, 740. 1H NMR (CDC13, ppm) : 7.92 (d, 2H), 7.80 (dd, 2H), 7.60 (d, 2H), 7.53 (dd, 2H), 7. 48-7. 32 (m, 46H), 7.16 (d, 2H)., 6. 85 (d, 4H), 6. 77 (d, 8H), 6. 72 (m, 6H), 6. 62 (t, 3H), 5.09 (s, 2H), 5.04 (s, 16H), 4.97 (s, 12H); FAB-Mass calcd. for C132H108O17 : 1964.76. Found: 1964 [Reaction Scheme 29]

Synthetic Example 54: Preparation of [G-4]- [AN-1]-C02H (Reaction Scheme 30) The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-4]- [AN-1] was used instead of [NA-1].

FT-IR (KBr, cm 1). 3300-2200 (very broad), 3032,2921, 1694, 1594, 1447, 1160, 1033, 743. 1H NMR (CDCl3, ppm) : 7.92 (d, 2H), 7.79 (dd, 2H), 7.61 (d, 2H), 7.52 (dd, 2H), 7.48-7. 30 (m, 86H), 7.14 (d, 2H), 6. 86 (d, 8H), 6.78 (d, 16H), 6.76 (m, 18H), 6.65 (t, 3H), 5.09 (s, 2H), 5.04 (s, 32H), 4.97 (s, 28H) ; FAB-Mass calcd. for C244H204033 : 3661.43 Found: 3661 [Reaction Scheme 30]

. Synthetic Example 55: Preparation of [G-1]-[NA-3]2-CO2H (Reaction Scheme 31) The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-1]- [NA-3] 2-CO2Me was used instead of [NA-3]2-CO2Me.

1H NMR (CDC13, ppm) : 7.92 (m, 4H), 7.62 (d, 4H), 7.56-7. 32 (m, 36H), 7.26 (d, 2H), 7.12 (d, 4H), 7.07 (t, 1H), 6.76 (d, 4H), 6. 58 (t, 2H), 5.30 (s, 4H), 5.09 (s, 4H), 5.02 (s, 8H) [Reaction Scheme 31] Synthetic Example 56: Preparation of [G-2]-[NA-3] 2-CO2H (Reaction Scheme 32) The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-2]- [NA-3]2-CO2Me was used instead of [NA-3] 2-CO2Me.

H NMR (CDC13, ppm) : 7. 92 (m, 4H), 7.62 (d, 4H), 7.52-7. 32 (m, 56H), 7.24 (d, 2H), 7.11 (d, 4H), 7.08 (t, 1H), 6.74 (d, 4H), 6. 70' (d, 8H), 6.58 (t, 6H), 5.31 (s, 4H), 5.09 (s, 4H), 5.04 (s, 16H), 4.98 (s, 8H) [Reaction Scheme 32]

Synthetic Example 57: Preparation of [G-3]- [NA-3] 2-CO2H (Reaction Scheme 33) The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-3]-[NA-3] 2-CO2Me was used instead of [NA-3]2-CO2Me.

1H NMR (CDC13, ppm) : 7.92 (m, 4H), 7.62 (d, 4H), 7.52-7. 32 (m, 96H), 7.24 (d, 2H), 7.11 (d, 4H), 7.08 (t, 1H), 6. 87. (d, 8H), 6.79 (d, 16H), 6.71 (m, 12H), 6.63 (t, 6H), 5.30 (s, 4H), 5.10 (s, 4H), 5.03 (s, 32H), 4. 99 (s, 24H) [Reaction Scheme 33] Synthetic Example 58: Preparation of [G-4]-[NA-3]2-CO2H (Reaction Scheme 34)

The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-4]- 2-CO2Me was used instead of [NA-3] 2-CO2Me.

H NMR (CDC13, ppm) : 7.92 (m, 4H), 7.62 (d, 4H), 7.52-7. 32 (m, 176H), 7.24 (d, 2H), 7.11 (d, 4H), 7.08 (t, 1H), 6.85 (d, 16H), 6.79 (d, 32H), 6. 73 (m, 36H), 6.62 (t, 6H), 5.30 (s, 4H), 5.09 (s, 4H), 5.04 (s, 64H), 4. 97 (s, 56H) [Reaction Scheme 34] Synthetic Example 59: Preparation of [G-1]-[AN-2]-CO2H (Reaction Scheme 35) The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-1]-[AN-2]-CO2Me was used instead of [AN-2] 2-CO2Me.

'H NMR (CDC13, ppm) : 7.95 (d, 4H), 7.98 (dd, 4H), 7.63 (d, 4H), 7.54 (dd, 4H), 7.52-7. 32 (m, 36H), 7.26 (d, 2H), 7.12 (d, 4H), 7.07 (t, 1H), 6.74 (d, 4H), 6.53 (t, 2H), 5.22 (s, 4H), 5.09 (s, 4H), 5.02 (s, 8H) [Reaction Scheme 35]

Synthetic Example 60: Preparation of [G-2]- [AN-2]-C02H (Reaction Scheme 36) The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-2]-[AN-2]-CO2Me was used instead of [AN-2] 2-CO2Me.

1H NMR (CDC13, ppm) # 7.95 (d, 4H), 7.96 (dd, 4H), 7.65 (d, 4H), 7.54 (dd, 4H), 7.49-7. 30 (m, 56H), 7.26 (d, 2H), 7.11 (d, 4H), 7. 08 (t, 1H), 6.77 (d, 4H), 6.69 (d, 8H), 6.55 (t, 6H), 5.31 (s, 4H), 5.11 (s, 4H), 5.06 (s, 16H), 4.97 (s, 8H) [Reaction Scheme 36] Synthetic Example 61: Preparation of [G-3]-[AN-2]-CO2H (Reaction Scheme 37) The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-3]-[AN-2]-CO2Me was used instead of [AN-2]2-CO2Me.

1H NMR (CDC13, ppm) : 7.97 (d, 4H), 7.95 (dd, 4H), 7.66 (d, 4H), 7. 54 (dd, 4H), 7. 50-7. 30 (m, 96H), 7. 26 (d, 2H), 7.10 (d, 4H), 7. 09 (t, 1H), 6. 87 (d, 8H), 6. 79 (d, 16H), 6. 72 (m, 12H), 6. 63 (t, 6H), 5.32 (s, 4H), 5.11 (s, 4H), 5.05 (s, 32H), 4.98 (s, 24H) [Reaction Scheme 37] Synthetic Example 62: Preparation of [G-4]-[AN-2]-CO2H (Reaction Scheme 38) The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-4]- [AN-2]-CO2Me was used instead of [AN-2] 2-C02Me.

IN NMR (CDC13, ppm) : 7.99 (d, 4H), 7.94 (dd, 4H), 7.65 (d, 4H), 7.54 (dd, 4H), 7.50-7. 30 (m, 176H), 7.26 (d, 2H), 7. 10 (d, 4H), 7. 09 (t, 1H), 6. 85 (d, 16H), 6. 79 (d, 32H), 6. 73 (m, 36H), 6.62 (t, 6H), 5. 30 (s, 4H), 5.10 (s, 4H), 5.07 (s, 64H), 4.99 (s, 56H) [Reaction Scheme 38]

Examples Example 1: Preparation of Yb3+-(C6H5COO-) 3 (Reaction Scheme 39) Into a flask which had been sufficiently dried under vacuum, 108 mg (2.7 mmol) of KH was charged under a nitrogen stream.

Into another flask, 300 mg (2.46 mmol) of benzoic acid was charged, and dissolved in 25 ml of THF. This solution was charged into the KH-containing flask by a cannula, and stirred until hydrogen gas was not generated. 5 ml of THF and 5 ml of EtOH were added to 229 mg (0.82 mmol) of anhydrous YbCl3. This solution was added to the potassium salt-containing mixture by a cannula and stirred for one day. After the solvent was removed under vacuum, the crude product was dried, washed several times with hexane and dried in vacuum to give the title compound.

Er3+- (C6H5COO-) 3 and Nd3+-(C6H5COO-)3 were also prepared in the same manner.

FT-IR (KBr, cm-1) : 1604,1418.

Yb3+-(C6H5COO-) 3 : Aem = 976 nm (Xex = 325 nm, solid state) Er3+-(C6H5COO-)3 : #em = 1540 nm (#ex = 325 nm, solid state) Nd3+- (C6H5COO-) 3 :llem = 886, 1054,1325 nm (apex-325 nm, solid state) Example 2: Preparation of Yb3+-(C6H5COO-)3 (Reaction Scheme 39)

The title compound was prepared in the same manner as in Example 1 except that pentafluorobenzoic acid was used instead of benzonic acid. Also, Er3+-(C6F5COO-)3 and Nd3+- (C6F5COO-) 3 were prepared in the same manner.

FT-IR (KBr, cm~l) : 1617, 1409.

Yb3+-(C6F5COO-)3 : #em = 976 nm (#ex = 325 nm, solid state) Er 3+_ (c6F5COO-) 3 : = 1540 nm (Aex = 325 nm, solid state) Nd3+- (C6F5COO-) 3 : = 886, 1054,1325 nm (#ex = 325 nm, solid state) [Reaction Scheme 39] Example 3 : Preparation of Yb3+- (C6H5COO-) 3 (bipyridine) (Reaction Scheme 40) The title compound was prepared in the same manner as in Example 1, using benzoic acid with the addition of anhydrous YbCl3 and 128 mg (0.82 mmol) of bipyridine. Also, Er3+- (C6H5COO-) 3 (bipyridine) and Nd3+-(C6H5COO-) 3 (bipyridine) were prepared in the same manner.

FT-IR (KBr, cm~l) 1) : 1600,1412.

Yb3+- (C6H5COO-) 3 (bipyridine) : Aem = 976 nm (#ex = 325 nm, solid state) Er3+-(C6H5COO-) 3 (bipyridine) : Aem = 1530 nm (#ex = 325 nm, solid state) Nd3+- (C6H5COO-) 3 (bipyridine) : Aem = 884,1055, 1324 nm (#ex = 325 nm, solid state)

Example 4: Preparation of Yb3+-(C6F5COO-)3(bipyridine) (Reaction Scheme 40) The title compound was prepared in the same manner as in Example 3 except that pentafluorobenzoic acid was used instead of benzoic acid. Also, Er3+- (C6F5COO-) 3 (bipyridine) 2 and Nd3+- (C6F5COO-) 3 (bipyridine) were prepared in the same manner.

FT-IR (KBr, cm- : 1587,1395.

Yb3+- (C6F5COO-) 3 (bipyridine) 976 nm (#ex = 325 nm, solid state) Er3+-(C6F5COO-) 3 (bipyridine) ? #em = 1517 nm (Aex = 325 nm, solid state) Nd3+- (C6F5COO-) 3 (bipyridine) : Aem = 884,1055, 1324 nm (29eX. = 325 nm, solid state) [Reaction Scheme 40] Ra Ra Ra Ra _ Ra Ra KH-LnCl3, bipyridine Ra Ra Ra Ra Ra Ra _ 2 Ra Ra 3 Tuf rua t Ra Ra Ra Ra THF/EtOH N 0 Ra is H or F Example 5: Yb3+-([NA-1]-CO2-) 3 (terpyridine) (Reaction Scheme 41) Into a flask which had been dried under vacuum, 56 mg (1.40 mmol) of KH, 300 mg (1.21 mmol) of [NA-1]-CO2H and 100 mg (0.42mmol) of terpyridine were charged under a nitrogen stream.

The mixture was dissolved in 100 ml of THF and stirred until hydrogen gas was not generated. In another flask, a small amount of methanol was added to 113 mg (0.40 mmol) of anhydrous YbCl3.

This solution was added to the potassium salt-containing mixture by a cannula and stirred for one day. After the solvent was removed under vacuum, the residue was dried, washed several

times with diethyl ether and dried in vacuum to give the title compound. Er3+-([NA-1]-CO2-) 3 (terpyridine) and Nd3+-([NA-l]-CO2-) 3 (terpyridine) were also prepared in the same manner.

Yb3+-([NA-1]-CO2-) 3 (terpyridine) : #em = 972 nm (#ex = 325 nm, solid state) Er3+-([NA-1]-CO2-) 3 (terpyridine) : Ae. 1530 nm (#ex = 325 nm, solid state) Nd3+-([NA-1]-CO2-)3(terpyridine) : #em = 888, 1053, 1324 nm (#ex = 325 nm, solid state) [Reaction Scheme 41] 0 ion 1 (KH/LnCls/terpyridine I [NA-1]-CO2H i'NF/MeOH N- / 3, N- Er3+ NA-11-CO2~) 3 (terpyridine) Example 6 : Preparation of Yb3+-([NA-2]-CO2-) 3 (terpyridine) (Reaction Scheme 42) The title compound was prepared in the same manner as in Example 5 except that [NA-2]-CO2H was used instead of [NA-1]-CO2H.

Also, Er3+-([NA-2]-C02-) 3 (terpyridine) and Nd3+-([NA-2]-CO2) 3 (terpyridine) were prepared in the same manner.

Yb3+-([NA-2]-CO2-) 3 (terpyridine) : Aem = 975 nm (#ex = 325 nm, solid state) Er3+-([NA-2]-CO2-) 3 (terpyridine) : 1530 nm (#ex = 325 nm, solid state) Nd3+-([NA-2]-CO2-) 3 (terpyridine) #em = 885, 1053,1324 nm (Aex = 325 nm, solid state) [Reaction Scheme 42] , nu 0 ion KH/LnCl3/terpyridine--O.. HaCO CO C-OH H, CO-Ln------N% THF MEDH o-- [NA-2]-CO2H Ln3+-([NA-21-CO2') 3 (terpyridine)

Example 7: Preparation of Yb3+-([NA-3] 2-CO2~) 3 (terpyridine) (Reaction Scheme 43) The title compound was prepared in the same manner as in Example 5 except that ([NA-3]) 2-CO2H was used instead of [NA-1]- C02H. Also, Er3+-([NA-3]2-CO2-) 3 (terpyridine) and Nd3+-([NA-3]-CO2- 3 (terpyridine) were prepared in the same manner.

Yb3+-([NA-3] 2-CO2~) 3 (terpyridine) : Aem = 975 nm (#ex = 325 nm, solid state) Er3+-([NA-3]2-CO2-) 3 (terpyridine) : 1530 nm (#ex = 325 nm, solid state) Nd3+-([NA-3]2-CO2-) 3 (terpyridine) #em = 885, 1054,1323 nm (#ex = 325 nm, solid state) [Reaction Scheme 43] /\/\ HsCO-, HCOO.-A- KH/LnCI/terpyridine THF/MeOH 0- .,,, J 3,,, ,, [NA-3] 2-CO2H Ln3*-NA-3-CO (L-12 2-Is (terpyridine) Example 8: Preparation of Yb3+-([NA-1]-CO2-) 3 (bipyridine) (Reaction Scheme 44) The title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine.

Also, Er3+-([NA-1]-CO2-) 3 (bipyridine) and Nd3+-([NA-l]-CO2) 3 (bipyridine) were prepared in the same manner.

Yb3+-([NA-1]-CO2-) 3 (bipyridine) : #em = 976 nm (#ex = 325 nm, solid state) Er3+-([NA-1]-CO2-) 3 (bipyridine) : Aem = 1530 nm (Xex = 325 nm, solid state) Nd3+-([NA-l]-CO2~) 3 (bipyridine) 885,1055, 1323 nm (#ex = 325 nm, solid state) [Reaction Scheme 44] KH/LnCl3/Bipyridine - 11 yridine 6 N- /Ln3"'j- C-OH [NA-IJ-COzH Ln- ( [NA-1]-C02') 3 (Bipyridine) 'Example 9: Preparation of Yb3+-([NA-2]-CO2-) 3 (bipyridine) (Reaction Scheme 45) The title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er3+-([NA-2]-CO2-) 3 (bipyridine) and Nd3+- ([NA-2]-CO2-) 3 (bipyridine) were prepared in the same manner.

Yb3+-([NA-2]-CO2-) 3 (bipyridine) : #em = 975 nm (#ex = 325 nm, solid state) Er3+-([NA-2]-CO2-) 3 (bipyridine) : Aem = 1530 nm (#ex = 325 nm, solid state) Nd3+-([NA-2]-CO2-) 3 (bipyridine) : #em = 885, 1053,1323 nm (#ex - 325 nm, solid state) [Reaction Scheme 45] zizi 0.. N w - KH/LnCI3IBipyridine - H3CO-H3CO-a %-3' - THF/MeOH O 3 [NA-2]-CO2H Ln3+-([NA-2]-CO2~) 3 (Bipyridine)

Example 10: Preparation of Yb3+-([NA-3]-C02-) 3 (bipyridine) (Reaction Scheme 46) The title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine.

Also, Er3+-([NA-3]-CO2) 3 (bipyridine) and Nd3+-([NA-3]-CO2-)3 (bipyridine) were prepared in the same manner.

Yb3+-([NA-3]2-CO2-) 3 (bipyridine) : #em = 975 nm (#ex = 325 nm, solid. state) Er3+-([NA-3] 2-CO2~) 3 (bipyridine) : 1532 nm (#ex = 325 nm, solid state) Nd3+-([NA-3]2-CO2-)3(bipyridine) : #em = 885, 1053,1323 nm (#ex = 325 nm, solid state) [Reaction Scheme 46] /\/\ H3CO-0-B, 0 KH/LnCl3/Bipyridine 0 O-..,. Nw CO, H ,----C L T O- H3C0 /\ H3C0 /\ \U/ H3Co <_O H3CO<_u 3/ [NA-312-CO2H Ln 3+. ( [NA-312-CO2-) 3 (Bipyricline) Example 11: Preparation of Yb3+-([AN-1]-CO2-)3 (terpyridine) (Reaction Scheme 47) The title compound was prepared in the same manner as in Example 5 except that [AN-1]-CO2H was used instead of [NA-1]-CO2H.

Also, Er3+-([AN-1]-CO2-) 3 (terpyridine) and Nd3+-([AN-1]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([AN-1]-CO2-) 3 (terpyridine) : #em = 976 nm (#ex = 442 nm, solid state) Er3+-([AN-1]-CO2-) 3 (terpyridine) : #em = 1531 nm (#ex = 442 nm, solid state) Nd3+-([AN-1]-CO2-) 3 (terpyridine) : Aem = 885, 1055 1324 nm (#ex = 442 nm, solid state) [Reaction Scheme 47] /\ y\ \/\ ° KH/LnC ! 3/terpyridine/r-\ -/=\, 0--.) =\ H3CO C-OH-- H3C0 c Ln, 3CO C n, / [AN-IK02H Ln 3+- ( [AN-11-CO2-) 3 (terpyridine) Example 12 : Preparation of Yb3+-([AN-2]-CO2-) 3 (terpyridine) (Reaction Scheme 48) The title compound was prepared in the same manner as in Example 5 except that [AN-2]-CO2H was used instead of [AN- 1]-CO2H. Also, Er3+-([AN-2]-CO2-) 3 (terpyridine) and Nd3+-([AN- 2]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([AN-2]2-CO2-) 3 (terpyridine) : #em = 976 nm (Aex = 442 nm, solid state) Er3+-([AN-2] 2-CO2~) 3 (terpyridine) : Aem = 1531 nm (Aex = 442 nm, solid state) Nd3+-([AN-2]2-CO2-) 3 (terpyridine) : Xem = 885, 1055,1324 nm 442 nm, solid state) [Reaction Scheme 48] H3CO H3CO H3C0 __\ i v i v H3 i v/v i v KH/LnCI3/terpyridine -C02H c Ln3 N THf :/MeOH H3C0 1/ H3C0 i / 3 0 '0 [AN-212-Co2H Ln3+. ( [AN-212-CO2-) 3 (terpyridine)

Example 13: Preparation of Yb3+-([AN-1]-CO2-)3 (bipyridine) (Reaction Scheme 49) The title compound was prepared in the same manner as in Example 5 except that [AN-1]-CO2H was used instead of [NA-1]-CO2H, and terpyridine was used instead of bipyridin. Also, Er3+-([AN- l]-C02") 3 (bipyridine) and Nd3+-([AN-1]-CO2-) 3 (bipyridine) were prepared in the same manner.

Yb3+-([AN-1]-CO2-) 3 (bipyri dine) Xe. 975 nm (#ex = 442 nm, solid state) Er3+-([AN-1]-CO2-) 3 (bipyridine) : #em = 1530 nm (#ex = 442 nm, solid state) Nd3+-([AN-1]-CO2-) 3 (bipyridine) : #em = 884, 1053,1324 nm (ex = 442 nm, solid state) [Reaction Scheme 49] 0 N - KWLnC131Bipyridine-O.. N H3CO C 0 Ln 3 THF/NbOH \/\/3 w [AN-lj-COzH Ln- ( [AN-- !]-C02') 3 (Bipyridine) Example 14: Preparation of Yb3+-([AN-2] 2-C°2-) 3 (bipyridine) (Reaction Scheme 50) The title compound was prepared in the same manner as in Example 5 except that [AN-2] 2-CO2H was used instead of [AN-1] 2-

C02H, and bipyridine was used instead of terpyridine. Also, Er3+- ([AN-2]2-CO2-) 3 (bipyridine) and Nd3+-([AN-2]2-CO2-] 3 (bipyridine) were prepared in the same manner.

Yb3+-([AN-2]2-CO2-) 3 (bipyridine) : Xem = 975 nm (apex 442 nm, solid state) Er3+-([AN-2]2-CO2-) 3 (bipyridine) : #em = 1530 nm (AeX = 442 nm, solid state) [Reaction Scheme 50] HsCO-- H, CO-0-) cl, H \/_. KH/LnCl3/Bipyridine \/o-i'3+'N\ H, CO H, CO 3 H3C0 v/v H3C0 v H3COv) 3 AJJ lAN-2l2-CO2H Ln3+-QAN-22-COa) 3 (Bipyridine) Example 15 : Preparation of Yb3+-([G-1]-[NA-2]-CO2-)3 (terpyridine) (Reaction Scheme 51) The title compound was prepared in the same manner as in Example 5 except that [G-1]-[NA-2]-CO2H was used instead of [NA- 1]-CO2H. Also, Er 3+_ ( [G-1]- [NA-21-C02-) 3 (terpyridine) and Nd3+- ([G-1]-[NA-2]-CO2-) 3 (terpyridine) are prepared in the same manner.

Yb3+-([G-1]-[NA-2]-CO2-)3(terpyridine) : #em = 976 nm (#ex = 325 nm, solid state) Er3+-([G-1]-[NA-2]-CO2-) 3 (terpyridine) : : #em = 1530 nm 325 nm, solid state) Nd3+-([[G-1]-[NA-2]-CO2-]3(terpyridine) : #em = 886, 1053,1324 nm (apex = 325 nm, solid state) [Reaction Scheme 51] nu ion KH/LnCI3/terpyridine R'C R'O C Lnl-----N, THF/MeOH -- O \/\/3 \/ Gz lNA-2] CO2H Ln3+-(lGW lNA-2]-CO2') 3 (terpyridine) R'= [G-11

Example 16: Preparation of YB3+-([G-2]-[NA-2]-CO2-) 3 (terpyridine) (Reaction Scheme 52) The title compound was prepared in the same manner as in Example 5 except that [G-2]-[NA-2]-CO2H was used instead of [NA- 1]-C02H. Also, Er3+-([G-2]-[NA-2]-CO2~) 3 (terpyridine) and Nd3+- ([G-2]-[NA-2]-CO2-)3 (terpyridine) were prepared in the same manner.

Yb3+-([G-2]-[NA-2]-CO2-) 3 (terpyridine) #em = 975 nm (AeX = 325 nm, solid state) Er3+-([G-2]-[NA-2]-CO2-) 3 (terpyridine) #em = 1530 nm (#ex = 325 nm, solid state) Nd3+-([G-2]-[NA-2]-CO2-) 3 (terpyridine) : #em = 886,1054, 1324 nm (ex = 325 nm, solid state) [Reaction Scheme 52] ,'\ 0 KH/LnCI31terpyridine 3, + -nu THF/MeOH ---'O ,, ,, J 3 vN_ N- [G-1]- [NA-2t-C02H Ln- ( [G-1]-tNA-2]-C02') 3 (terpyridine) R'= [G-2] Example 17: Preparation of Yb3+-([G-3]-[NA-2]-C02) 3 (terpyridine) (Reaction Scheme 53)

The title compound was prepared in the same manner as in Example 5 except that [G-3]-[NA-2]-CO2H was used instead of [NA- 1]-CO2H. Also, Er 3+- ( [G-31- [NA-21-CO2-) 3 (terpyridine) and Nd3+- ( [G-3]- [NA-2]-C02-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-3]-[NA-2]-CO2-) 3 (terpyridine) #em = 976 nm (Aex = 325 nm, solid state) Er3+-([G-3]-[NA-2]-CO2-) 3 (terpyridine) #em = 1530 nm (#ex = 325 nm, solid state) Nd3+-([G-3]-[NA-2]-CO2-) 3 (terpyridine) : #em = 886,1053, 1324 nm (#ex = 325 nm, solid state) [Reaction Scheme 53] zu ., N KH/LnCl3/terpyridine-, - R'o C-OH R'O C,-Ln N U THF/MeOH --,O ' G-31-lNA-2]-CO2H Ln3+-(1G-3]-[NA-21-C02-) 3 (terpyridine) R'= lG-3] Example 18: Preparation of Yb3+-([G-4]-[NA-2]-CO2-) 3 (terpyridine) (Reaction Scheme 54) The title compound was prepared in the same manner as in Example 5 except that [G-4]-[NA-2]-CO2H was used instead of [NA-1]-CO2H. Also, Er3+-([G-4]-[NA-2]-CO2-) 3 (terpyridine) and Nd3+-([G-4]-[NA-2]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-4]-[NA-2]-CO2) 3 (terpyridine) #em = 976 nm (#ex = 325 nm, solid state) Er3+-([G-4]-[NA-2]-CO2) 3 (terpyridine) #em = 1530 nm (#ex = 325 nm, solid state) Nd3+- [G-4]-[NA-2]-CO2~) 3 (terpyridine) : Aem = 885,1054, 1325 nm (#ex = 325 nm, solid state) [Reaction Scheme 54]

N 101 KH/LnC [3/terPyridine U THF/MeOH -- O /3 N- [G-41-ENA-21-CO2H Ln 3+_ ( [G-4]- [NA-2]-CO2") 3 (terpyridine) R'= [G-4] Example 19: Preparation of Yb3+-([G-1]-[NA-3]2-CO2-) 3 (terpyridine) (Reaction Scheme 55) The title compound was prepared in the same manner as in Example 5 except that [G-1]-[NA-3] 2-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-l]-[NA-3] 2-CO2~) 3 (terpyridine) and Nd3+- ([G-1]-[NA-3]2-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-1]-[NA-3]2-CO2-) 3 (terpyridine) #em = 975 nm (#ex = 325 nm, solid state) Er3+-([G-1]-[NA-3]2-CO2-) 3 (terpyridine): #em = 1532 nm (#ex = 325 nm, solid state) Nd3+-([G-1]-[NA-3]2-CO2-) 3 (terpyridine) #em = 885,1053, 1324 nm (2.. = 325 nm, solid state) [Reaction Scheme 55] N \ i i KH/LnCI/terpyridine o O- \-/C02H Ln !'t----N THF/MeOH Q R i v r v R0 r v r v R'O R'O N- [G-1]-[NA-3] 2-Co2H Ln3+ (1G-1]-[NA-3] 2-CO2-) 3 (terpyridine) R'= lG-1]

Example 20 : Preparation of Yb3+-([G-2]-[NA-3] 2-CO2) 3 (terpyridine) (Reaction Scheme 56) The title compound was prepared in the same manner as in Example 5 except that [G-2]-[NA-3] 2-CO2H was used instead of [NA-1]-CO2H. Also, Er3+-([G-2]-[NA-3]2-CO2-)3 (terpyridine) and Nd3+-([G-2]-[NA-3]2-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-2]-[NA-3] 2-co2) 3 (terpyridine) #em = 976 nm (Aex = 325 nm, solid state) Er3+-([G-2]-[NA-3]2-CO2-) 3 (terpyridine): Aem = 1532 nm (Aex = 325 nm, solid state) Nd3+-([G-2]-[NA-3]2-CO2-) 3 (terpyridine) :Aem = 886,1053, 1324 nm (Xex = 325 nm, solid state) [Reaction Scheme 56] R'O N KHlLnCl3/terpyridine 4 0 THF/MeOH 0 0- R'O R'O w i 3 \/ 3 [G-21-[NA-3] 2-CO2H Ln3 G-2]-[NA-3l2-CO2-) 3 (terpyridine) R'= [G-2] Example 21: Preparation of Yb3+-([G-3]-[NA-3]2-CO2-) 3 (terpyridine) (Reaction Scheme 57) The title compound was prepared in the same manner as in Example 5 except that [G-3]-[NA-3] 2-CO2H was used instead of [NA-1]-CO2H. Also, Er3+-([G-3]-[NA-3]2-CO2-) 3 (terpyridine)

and Nd3+-([G-3)-[NA-3]2-CO2-)3 (terpyridine) were prepared in the same manner.

Yb3+-([G-3]-[NA-3] 2-CO2) 3 (terpyridine) : #em = 976 nm (#ex = 325 nm, solid state) Er3+-([G-3)-[NA-3]2-CO2-) 3 (terpyridine): #em = 1532 nm (#ex = 325 nm, solid state) Nd3+-([G-3]-[NA-3]2-CO2-) 3 (terpyridine) :Aem = 886,1054, 1324 nm (#ex = 325 nm, solid state) [Reaction Scheme 57] N R'O---0"IN 0 KH/LnCb/terpyridine KH/LnCI/terpyridine , O.'- R'O v _ {3< _ 3 t N\ R, Q r v i v R r v r v v i v i 3 \ l [G-3]-[NA-3] 2-CO2H Ln3+-([G-3]-[NA-3] 2-CO2-) 3 (terpyridine) R'= [G-3] Example 22: Preparation of Yb3+-([G-4]-[NA-3]2-CO2-) 3 (terpyridine) (Reaction Scheme 58) The title compound was prepared in the same manner as in Example 5 except that [G-4]- [NA-3] 2-CO2H was used instead of [NA-l]-CO2H. Also, Er3+-([G-3]-[NA-4] 2-CO2~) 3 (terpyridine) and Nd3+-([G-4]-[NA-3]2-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+- (. [G-4]- [NA-3] 2-CO2-) 3 (terpyridine) #em = 976 nm (#ex = 325 nm, solid state) Er3+-([G-4]-[NA-3]2-CO2-) 3 (terpyridine): #em = 1531 nm (ex = 325 nm, solid state) Nd3+-([G-4]-[NA-3]2-CO2-) 3 (terpyridine) : #em = 885, 1054, 1324 nm (Aex = 325 nm, solid state) [Reaction Scheme 58] N -N 0 KH/LnC131terpy (idine 0-. Q" THP/MeOH o- \ / T-- =-- i i 3 \ l [G-4]-lNA-3] 2-CO2H Ln3 G-41-[NA-312-C02-) 3 (terpyridine) R'= [G-4]

. Example 23: Preparation of Yb3+-([G-1]-[AN-1]-CO2-) 3 (terpyridine) (Reaction Scheme 59) The title compound was prepared in the same manner as in Example 5 except that [G-1]- [AN-1]-C02H was used instead of [NA-1]-C02H. Also, Er 3+_ ( [G-1]- [AN-I]-CO2-) 3 (terpyridine) and Nd3+-([G-1]-[AN-1]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-1]-[AN-1]-CO2-) 3 (terpyridine) : Aem = 975 nr (AeX = 442 nm, solid state) Er3+-([G-1]-[AN-1]-CO2-) 3 (terpyridine) : Aem = 1530 nn (AeX = 442 nm, solid state) Nd3+-([G-1]-[AN-1]-CO2-) 3 (terpyridine) : #em = 885,1054, 1325 nm (Aex = 442 nm, solid state) [Reaction Scheme 59] /\ IN R'O C-OH R'O C, Ln,--N U THF/MeOH GF lAN-1]-CO2H Ln3+ G-1]-lAN-1]-CO2") 3 (terpyridine) R'= [G-1] Example 24 : Preparation of Yb3+-([G-l]-[AN-l]-C02) 3 (terpyridine) (Reaction Scheme 60)

The title compound was prepared in the same manner as in Example 5 except that [G-2]-[AN-1]-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-2]-[AN-1]-CO2-) 3 (terpyridine) and Nd3+- ([G-2]-[AN-1]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-2]-[AN-1]-CO2-) 3 (terpyridine) : rem = 976 nm (#ex = 442 nm, solid state) Er3+-([G-2]-[AN-l]-CO2) 3 (terpyridine) #em = 1530 nm (#ex = 442 nm, solid state) Nd3+-([G-2]-[AN-1]-CO2-) 3 (terpyridine) : #em = 886, 1054,1325 nm (AeX = 442 nm, solid state) [Reaction Scheme 60] ion KH/LnCI3/terpyridine R'O C70H R'O do-Lni+---N, THF/MeOH 3 N- [G-2]- AN-1]-CO2H Ln3 | G-2]-[AN-1]-CO2) 3 (terpyridine) Fr = [G-2] Example 25: Preparation of Yb3+-([G-3]-[AN-1]-CO2-)3 (terpyridine) (Reaction Scheme 61) The title compound was prepared in the same manner as in Example 5 except that [G-3]-[AN-1]-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-3]-[AN-1]-CO2-) 3 (terpyridine) and Nd3+- ([G-3]-[AN-1]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-3]-[AN-1]-CO2-)3(terpyridine) : #em = 975 nm (#ex = 442 nm, solid state) Er3+-([G-3]-[AN-l]-CO2) 3 (terpyridine) #em = 1531 nm (#ex = 442 nm, solid state) Nd3+-([G-3]-[AN-1]-CO2-) 3 (terpyridine) : Aem = 884,1052, 1324 nm (#ex = 442 nm, solid state) [Reaction Scheme 61] /\/\ 0 KHILnCI3/terpyridin-e p N R'O C-OH RO C Ln,----N THF/MeOH -J Q [G-3]- [AN-1]-C02H Ln- ( [G-3]- [AN-1]-C02') 3 (terpyridine) R'= lez

Example 26 : Preparation of Yb3+-([G-4]-[AN-l]-CO2) 3 (terpyridine) (Reaction Scheme 62) The title compound was prepared in the same manner as in Example 5 except that [G-4]-[AN-1]-CO2H was used instead of [NA-1]-CO2H. Also, Er3+-([G-4]-[AN-1]-CO2-) 3 (terpyridine) and Nd3+-([G-4]-[AN-1]-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-4]-[AN-l]-CO2) 3 (terpyridine) : #em = 976 nm (#ex = 442 nm, solid state) Er3+-([G-4]-[AN-l]-CO2~) 3 (terpyridine) #em = 1530 nm (#ex = 442 nm, solid state) Nd3+-([G-4]-[AN-l]-CO2~) 3 (terpyridine) : Aem = 884, 1052,1325 nm (#ex = 442 nm, solid state) [Reaction Scheme 62] IN KHILnCllter ridine-'-- /\"THF/MeOH y==\"-'0 \./-" - THFIMeOH \/\/3 \/ [G-3]- 1]-C02H Ln3+-([G 3]-lAN-1]-C02") 3 (terpyridine) R'= [G-4]

Example 27: Preparation of Yb3+-([G-1]-[AN-2]2-CO2-) 3 (terpyridine) (Reaction Scheme 63) The title compound was prepared in the same manner as in Example 5 except that [G-1] - [AN-2]2-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-1]-[AN-2]2-CO2-) 3 (terpyridine) and Nd3+- ([G-1]-[AN-2] 2-CO2-) 3 (t. erpyridine) were prepared in the same manner.

Yb3+-([G-1]-[AN-2]2-CO2-) 3 (terpyridine) : #em = 975 nm (, \ex = 442 nm, solid state) Er3+-([G-1]-[AN-2]2-CO2-) 3 (terpyridine) : Rem = 1531 nm (# 442 nm, solid state) Nd3+-([G-1]-[AN-2]2-CO2-) 3 (terpyridine) : #em = 884,1054, 1324 nm (hex = 442 nm, solid state) [Re. action Scheme 631 <\ H H3CO N ICHILnCl3/terpyddine o, 0...' 3. THF/MeOH o- \ H3CO v H3COw 3 t 3- \/\/ [6 ;-33W [AN-2] 2-CO2H Ln3}-([G-3]-tAN-2] 2-CO2-) 3 (terpyridine) R'= tG-1] Example 28 : Preparation of Yb3+-([G-2]-[AN-2]2-CO2-) 3 (terpyridine) (Reaction Scheme 64) The title compound was prepared in the same manner as in Example 5 except that [G-2]-[AN-2] 2-CO2H was used instead of [NA-1]-C02H. Also, Er3+-([G-2]-[AN-2] 2-CO2~) 3 (terpyridine) and Nd3+-([G-2]-[AN-2]2-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-2]-[AN-2]2-CO2-) 3 (terpyridine) #em = 975 nm (#ex = 442 nm, solid state) Er3+-([G-2]-[AN-2]2-CO2-) 3 (terpyridine): #em = 1531 nm 442 nm, solid state) Nd3+-([G-2]-[AN-2]2-CO2-) 3 (terpyridine) : #em = 886,1053, 1325 nm (#ex = 442 nm, solid state) [Reaction Scheme 64] /\/\ 0 K ILnCl3/terpyridine C02H------ CO H'fHF/MeOH "'Ln H3C H3CO N- L 3 [G-3]-lAN-2] 2-C02H Ln3+-([G-3]-lAN-2] 2-CO2-) 3 (terpyridine) R'= [G-2] Example 29 : Preparation of Yb3+-([G-3)-[AN-2]2-CO2-)3 (terpyridine) (Reaction Scheme 65) The title compound was prepared in the same manner as in Example 5 except that [G-3]-[AN-2] 2-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-3]-[AN-2] 2-CO2) 3 (terpyridine) and Nd3+- ([G-3]-[AN-2]2-CO2-) 3 (terpyridine) were prepared in the same manner.

YB3+-([G-3]-[AN-2]2-CO2-) 3 (terpyridine) : #em = 975 nm (#ex = 442 nm, solid state) Er3+-([G-3]-[AN-2] 2-CO2) 3 (terpyridine) : Aem = 1531 nm (apex-442 nm, solid state) Nd3+-([G-3]-[AN-2]2-CO2-) 3 (terpyridine) : Aem = 885,1054, 1325 nm (#ex = 442 nm, solid state) [Reaction Scheme 65] o o'/=\ H3C0 v i v i v H3 i v i v i v KH/LnCl3/terpyridine THF/MeOH H3C0 v i v H i v i v 0 vi vi 3, \ l [G-3]- [AN-2] 2-C02H Ln- ( [G-3]- [AN-2] 2-COz-) 3 (terpyridine) R'= [G-31

Example 30: Preparation of Yb3+-([G-4]-[AN-2]2-CO2-) 3 (terpyridine) (Reaction Scheme 66) The title compound was prepared in the same manner as in Example 5 except that [G-4]-[AN-2] 2-CO2H was used instead of [NA- 1]-CO2H. Also, Er3+-([G-4]-[AN-2]2-CO2-) 3 (terpyridine) and Nd3+- ([G-4]-[AN-2]2-CO2-) 3 (terpyridine) were prepared in the same manner.

Yb3+-([G-4]-[AN-2]2-CO2-) 3 (terpyridine) 976 nm (AeX = 442 nm, solid state) Er3+-([G-4]-[AN-2]2-CO2-) 3 (terpyridine): Rem = 1531 nm (#ex = 442 nm, solid. state) Nd3+-([G-4]-[AN-2]2-CO2-) 3 (terpyridine) : Aem = 884,1053, 1324 nm (#ex = 442 nm, solid state) [Reaction Scheme 66] /\/\ l v i v i v H3/v i v/v ($Co2H TllF/MeOII | $ b H3CO + 4 O N\-/ THF/MeOH /v/3 / zig [AN-2] 2-C02H Ln3+- ( [G-4]- [AN-2] 2-CO2-) 3 (terpyridine) R'= [G-4] Example 31: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO-)] 3 (Reaction Scheme 67)

The title compound was prepared in the same manner as in Example 1, using 5,10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin.

Also, Er3+-[porphyrin(phenyl)3(COO-)]3 and Nd3+- [porphyrin(phenyl)3(COO-)]3 were prepared in the same manner.

FT-IR (KBr, cm-1) : 3316,1596, 1402.

Yb3+- [porphyrin (phenyl) 3 (COO-)] 3 #em = 975 nm (#ex = 442 nm, solid state) <BR> <BR> <BR> <BR> Er3+-[porphyrin(phenyl)3(COO-)]3 : #em = 1455 nm (#ex = 442 nm, solid state) Nd3+-[porphyrin(phenyl) 3 (COO-)] 3 : Aem = 885, 1054,1323 nm (AeX = 442 nm, solid state) [Reaction Scheme 67] Example 32: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO~ ) zinc] 3 (Reaction Scheme 68) The title compound was prepared in the same manner as in Example 1 except that [5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zince was used instead of 5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO~) zinc] 3 and Nd3+-[porphyrin (phenyl) 3 (COO- ) zinc] 3 were prepared in the same manner.

FT-IR (KBr, cm- : 1596,1410 Yb3+-[porphyrin (phenyl) 3 (. COO-) zinc] 3 : #em = 975 nm (#ex = 442 nm, solid state)

Er3+-[porphyrin (phenyl) 3 (COO-) zinc]3 : #em = 1520 nm (Xex = 442 nm, solid state) Nd3+- [porphyrin (phenyl) 3 (COO~) zinc] 3 : #em = 885, 1054, 1323. nm (#ex = 442 nm, solid state) Example 33: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- ) platinum] 3 (Reaction Scheme 68) The title compound was prepared in the same manner as in Example 1 except that [5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum was used instead of 5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO-) platinum] 3 and Nd3+- [porphyrin (phenyl) 3 (COO-) platinum] 3 were prepared in the same manner.

FT-IR (KBr, cm.-1). 1599,1417.

Yb3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 : Aem =975 nm (#ex = 442 nm, solid state) Er3+-[porphyrin (phenyl) 3 (COO~) platinum] 3: Aem =1520 nm (#ex = 442 nm, solid state) Nd3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 : Xem = 885, 1054, 1323 nm (#ex = 442 nm, solid state) [Reaction Scheme 68]

Example 34: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) (Reaction Scheme 69) The title compound was prepared in the same manner as in Example 3, using 5,10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin, with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+- [porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) and Nd3+- [porphyrin (phenyl) 3 (COO-) 13 (bipyridine) were prepared in the same manner.

FT-IR (KBr, cm- : 3310,1599, 1400.

Yb3+-[porphyrin (phenyl) 3 (COO-)]3(bipyridine) : #em = 975 nm (# 442 nm, solid state) Er- [porphyrin (phenyl)- ; (COO")] 3 (bipyridine): Aem =1520nm (Aex =442 nm, solid state) Nd3+-[porphyrin(phenyl)3(COO-)]3(bipyridine) : #em = 885, 1054, 1323 nm (AeX = 442 nm, solid state) [Reaction Scheme 69] if i IN HN 1 11 /\ . N HN -, KH/Bipy NH N. -p +.. N/ 'I, NH N-\ LnCl3/THFIEtOH _N HN \/ Ln3''N t/3 i i I COOH Example 35: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- ) zinc] 3 (bipyridine) (Reaction Scheme 70) The title compound was prepared in the same manner as in Example 3 except that [5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc was used instead of 5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) and Nd3+-

[porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) were prepared in the same manner.

FT-IR (KBr, cm-1) : 1600,1401.

Yb3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine): #em =978 nm (#ex = 442 nm, solid state) Er3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine): #em =1522nm (#ex = 442 nm, solid. state) Nd3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 890, 1052, 1323 nm (#ex = 442 nm, solid state) Example 36: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- ) platinum] 3 (bipyridine) (Reaction Scheme 70) The title compound was prepared in the same manner as in Example 3 except that [5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum was used instead of 5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) and Nd3+- [porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) were prepared in the same manner.

FT-IR (KBr, cm-') : 1599,1410.

Yb3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem =978nm(#ex =442 nm, solid state) Er3+-[porphyrin(phenyl) 3 (COO-) platinum] 3 (bipyridine): #em =1524nm (Aex=442nm, solid state) Nd3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) #em = 890, 1052,1323 nm (Aex = 442 nm, solid state) [Reaction Scheme 70] X i'X I I I 3 / I N N -KH/Bipy /N. : N \-O * -N/ \/LnC131THF/EtOH _NM. N \ \/, Ln3.,,, N \. i// / /I I 3 I COOH

MisZnorPt Example 37: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- )] 3 (terpyridine) (Reaction Scheme 71) The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.

Also, Er3+-[porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) and Nd3+- [porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) were prepared in the same manner.

FT-IR (KBr, cm-1) : 3314,1604, 1405.

3+_-) 13 (terpyridine): Aem =978nm (Aex =442 nm, solid state) Er3+-[porphyrin (phenyl) 3 (COO-)] 3 (terpyridine): Aem =1428nm (#ex =442nm, solid state) Nd3+-[porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) #em = 890, 1052, 1323 nm (#ex = 442 nm, solid state) [Reaction Scheme 71] . I I Nui /N HN -KH I Terpy NH N -p 3 _ NH N-\/LnCly I THF I EtOH _ N HN i/ , N- i i I 3 w I COOH

Example 38 : Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- ) zinc] 3 (terpyridine) (Reaction Scheme 72) The title compound was prepared in the same manner as in Example 3 except that [5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc was used instead of [5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) and Nd3+- [porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) were prepared in the same manner.

FT-IR (KBr, cm-1) : 1600,1402.

Yb3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : rem 978 nm (#ex = 442 nm, solid state) Er3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) #em = 1520 nm (#ex = 442 nm, solid state)- Nd3+-[porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : #em = 890,1052, 1323 nm (Xex = 442 nm, solid state) Example 39: Preparation of Yb3+-[porphyrin (phenyl) 3 (COO- ) platinum] 3 (terpyridine) (Reaction Scheme 72) The title compound was prepared in the same manner as in Example 3 except that ( [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum) was used instead of [5,10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) and Nd3+- [porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) were prepared in the same manner.

FT-IR (KBr, cm-1) : 1598,1408.

Yb3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) #em = 978 nm (AeX = 442 nm, solid state)

Er3+-[porphyrin (phenyl) 3 (C00-) platinum] 3 (terpyridine) #em = 1524 nm (#ex = 442 nm, solid state) Nd3+-[porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) rem-890, 1052, 1323 nm (#ex = 442 nm, solid state) [Reaction Scheme 72] N IN N KH I Terpy N, N 0 i/_/\ _ w w,, N- 3 COOH M is Zn or Pt Example 40 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-)] 3 (Reaction Scheme 73) The title compound was prepared in the same manner as in Example 1, using [G-1] 3-5,10, 15-triphenyl-20- (4- carboxymethyl) porphyrin. Also, Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO-)]3 and Nd3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-)] 3were prepared in the same manner.

Yb3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)] 3 : #em = 975 nm (#ex = 442 nm,. solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)] 3 : #em = 1455 nm (#ex = 442 nm, solid state) Nd3+-[[G-1]3-porphyrin(phenyl) 3 (COO-)] 3 : #em = 885, 1054,1323 nm (Aex = 442 nm, solid state) Example 41 : Preparation of Yb3+-[[G-2]3- porphyrin (phenyl) 3 (COO-)]3 (Reaction Scheme 73)

The title compound was prepared in the same manner as in Example 1, using [G-2]3-5,10,15-triphenyl-20-(4- carboxyphenyl) porphyrin. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-)] 3 and Nd [G-213-porphyrin (phenyl) 3 (COO- )] 3 were prepared in the same manner.

Yb3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) ]3 : #em = 975 nm 442 nm, solid state) #ex = (phenyl) 3 (COO-) 3 : Aem = 1455 nm Er3+-[[G-2]3-porphyrin nm,. solid state) (#ex = 442 (phenyl) 3 Nd3+-[[G-2]3-porphyrin 3 : Aem = 885,1054, 1323 nm (Aex = 442 nm, solid state) (COO-)] : Example 42 porphyrin (phenyl) 3 Preparation of Yb3+-[[G-3]3-$(COO-)] 3 (Reaction Scheme 73) The title compound was prepared in the same manner as in Example 1, using [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er3+-[[G-3]3- porphyrin (phenyl) 3 (COO-)] 3 and Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO- ) 3 were prepared in the same manner.

Yb3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 : Aem = 975 nm (AeX = 442 nm, solid state) Er3+-[[G-3]3-porphyrin (phenyl) 3 (CO,-)] 3 : #em = 1455 nm (#ex = 442 nm, solid state) Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 : #em = 885, 1054, 1323 nm (#ex = 442 nm, solid state) Example 43 : Preparation of Yb 3+-L [G-413- porphyrin (phenyl) 3 (COO-)] 3 (Reaction Scheme 73) The title compound was prepared in the same manner as in Example 1, using [G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er3+-[[G-4]3-

porphyrin (phenyl) 3 (COO-)] 3 and Nd3+-[[G-4]3-porphyrin (phenyl) 3 (COO- ) 3 were prepared in the same manner.

Yb3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-)] 3 : # em = 975 nm (Aex = 442 nm, solid state) Er3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-)] 3 #em = 1455 nm (#ex = 442 nm, solid state) Nd3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)]3 : # em = 885, 1054,1323 nm (AeX = 442 nm, solid state) [Reaction Scheme 73] Example 44 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (Reaction Scheme 74) * The title compound was prepared in the same manner as in Example 1, using [[G-1] 3-5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zince. Also, Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 and Nd3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 were prepared in the same manner. <BR> <BR> <P>Yb3+-[[G-1]3-porphyrin(phenyl)3(COO-)zinc]3 : #em = 975 nm (#ex = 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 #em = 1520 nm 442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 : #em = 885,1054, 1323 nm (#ex = 442 nm, solid state)

Example 45 : Preparation of Yb3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [[G-2]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 and Nd3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 were prepared in the same manner.

Yb3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 #em = 975 nm 442 nm, solid state) Er3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) zinc]3 : #em = 152- nm (#ex = 442 nm, solid state) Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 : #em = 885, 1054,1323 nm (#ex = 442 nm, solid state) Example 46 : Preparation of Yb3+-[[G-3] 3- porphyrin (phenyl) 3 (COO-) zinc] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 and Nd3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 were prepared in the same manner.

Yb3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 : Xem = 975 nm (#ex = 442 nm, solid state) Er3+-[[G-3]3-porphyrin(phenyl)3(COO-) zinc] 3 : Xem = 1520 nm (#ex = 442 nm, solid state) Nd3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 : #em = 885, 1054,1323 nm (#ex = 442 nm, solid state) Example 47 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (Reaction Scheme 74)

The title compound was prepared in the same manner as in Example 1, using [ [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-4] 3- porphyrin (phenyl) 3 (COO-) zinc] 3 and Nd3+-[[G-4] 3- porphyrin (phenyl) 3 (COO-) zinc] 3 were prepared in the same amnner.

YB3+-[[G-4]3-porphyrin (phenyl) 3 (COO-) zinc] 3 : 975 nm (#ex = 442 nm, solid state) Er3+-[[G-4]3-porphyrin(phenyl) 3 (COO-) zinc] 3 #em = 1520 nm (Aex = 442 nm, solid state) Nd3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 : #em = 885, 1054,1323 nm (#ex = 442 nm, solid state) Example48 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [[G-1] 3-5,10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO") platinum] 3 and Nd3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 were prepared in the same manner.

Yb3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 : #em = 975 nm (#ex = 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 : #em = 1520 nm (#ex = 442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 : Aem = 885, 1054, 1323 nm (#ex = 442 nm, solid state) Example 49: Preparation of Yb3+-[[G-2]3= porphyrin (phenyl) 3 (COO-) platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [[G-2]3-5, 10, 15-triphenyl-20- (4-

carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) platinum 3 and Nd3+-[[G-233- porphyrin (phenyl) 3 (COO-) platinum] 3 were prepared in the same manner.

Yb3+-[[G-2]3-porphyrin (phenyl) j (COO-) platinum] 3 : #em = 975 nm (#ex = 442 nm, solid state) Er3+-[[G-2]3-porphyrin(phenyl) 3 (COO-) platinum] 3 : Aem= 1520 nm (Xex = 442 nm, solid state) Nd3+-[[G-2]3-porphyrin(phenyl) 3 (COO-) platinum] 3 : Aem = 885, 1054, 1323 nm (#ex = 442 nm solid state) Example 50: Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3 (COO-)platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porpnyrin] platinum. Also, Er3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) platinum] 3 and Nd3+-[[G-333- porphyrin (phenyl) 3 (COO-) platinum33 were prepared in the same manner.

Yb3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) platinum] 3 : Aem = 975 nm (Aex = 442 nm, solid state) Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO') platinum] 3 : Aem = 1520 nm (apex = 442 solid state) Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)platinum]3 : #em = 885, 1054, 1323 nm (#ex = 442 nm, solid state) Example 51 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [[G-4]3-5, 10, 15-triphenyl-20- (4- ca-*boxyphenyl) porphyrin] platinum. Also, Er3+-[[G-4]3-

porphyrin (phenyl) 3 (COO-) platinum] 3 and Nd3+-[[G-4] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 were prepared in the same manner~ Yb3+-[[G-4]3-porphyrin (phenyl) 3 (COO-) platinum] 3 : #em = 975 nm = 442 nm, solid state) Er3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 : #em = 1520 nm (#ex = 442 nm, solid state) Nd3+- [. [G-4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 : #em = 885, 1054, 1323 nm (apex = 442 nm, solid state) [Reaction Scheme 74] Example 52 : Preparation of Yb3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) (Reaction Scheme 75) The title compound was prepared in the same manner as in Example 3, using [G-1] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) and Nd3+-[[G-1] 3-Porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-1]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) #em = 975 nm (Aex = 442 nm, solid state) Er3+-[[G-1]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) 1520 nm (#ex = 442 nm, solid state)

Nd3+-[[G-1] 3-porphyrinphenyl) 3 (COO-)] 3 (bipyridine) : Aem = 885, 1054,1323 nm (AeX = 442 nm, solid state) Example 53 : Preparation of Yb 3+_ [G-213- porphyrin (phenyl) 3 (COO- The title compound was prepared in the same manner as in Example 3, using [G-2] 3-5, 10, 15-Triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+-[[G-2] 3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) and Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) were prepared in the same manner.

YB3+-[[G-2]3-porphyrin (phenyl) 3 (COO-)]3(bipyridine) : #em = 975 nm (AeX = 442 nm, solid state) Er3+-[[G-2]3-porphyrin(phenyl) 3 (COO-)] 3 (bipyridine) : #em = 1520 nm (#ex = 442 nm, solid state) Nd3+-[[G-2]3-porphyrin (phenyl) 3 (COO-)3(bipyridine) : #em = 885, 1054, 1323 nm (#ex = 442 nm, solid state) Example 54: Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) (Reaction Scheme 75) . The title compound was prepared in the same manner as in Example 3, using [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) and Nd3+-[[G-3] 3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) Aem-97 5 nm (#ex = 442 nm, solid state) Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)]3(bipyridine) : #em = 1520 nm (#ex = 442 nm, solid state)

Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) #em = 885, 1054,1323 nm (#ex = 442 nm, solid state) Example 55 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) (Reaction Scheme 75) The title compound was prepared in the same manner as in Example 3, using [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+-[[G-4]3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) and Nd3+-[[G-4] 3-porphyrin (phenyl) 3 (COO- )] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) #em = 975 nm (AeX = 442 nm, solid state) ER3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) 1520 nm (#ex = 442 nm, solid state) Nd3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)] 3 (bipyridine) #em = 885, 1054,1323 nm (Aex = 442 nm, solid state) [Reaction Scheme 75] oz [Gn] [Gn] sO if [Gn]/N HN _ /\/''KH I BIPY O/\/NH N \ . Ln3 ; N i [Gn] O LnCIs THF EtOH t [Dn] /, e V L l \ s i a COOH O. IGn1 Example 56 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) (Reaction Scheme 76) . The title compound was prepared in the same manner as in Example 3, using [[G-1] 3-5,10, 15-triphenyl-20- (4-

carboxyphenyl) porphyrin] zinc. Also, Er3+[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc]3 (bipyridine) and Nd3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) were prepared in the same manner.

By3+-[[G-1]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : Xem = 978 nm (#ex = 442 nm, solid state) ER3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : =1522 nm (#ex =442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : Xem =890, 1052,1323 nm (ÅeX =442 nm, solid state) Example 57 : Preparation of Yb3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [[G-2]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) and Nd3+-[[G-2] 3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) were synthesized in the same manner.

Yb3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : 978 nm (#ex = 442 nm, solid state) Er3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 1522 nm (#ex = 442 nm, solid state) Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : = 890, 1052,1323 nm (#ex = 442 nm, solid state) Example 58: Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as Example 3, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphypin] zinc. Also, Er3+-[[G-3]3-

porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) and Nd3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) were synthesized in the same manner.

Yb3+-[[G-333-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : Aem = 978 nm (#ex = 442 nm, solid state) Er3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 1522 nm (#ex = 442 nm, solid state) Nd3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 890, 1052, 1323 nm (#ex = 442 nm, solid state) Example 59 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example, using [ [G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) and Nd3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-4]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 978 nm (Aex = 442 nm, solid state) Er3+-[[G-4]3-porphyrin (phenyl)- 3 (COO-) zinc] 3 (bipyridine) : Aem = 1522 nm (Aex = 442 nm, solid state) Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (bipyridine) : #em = 890, 1052, 1323 nm (#ex = 442 nm, solid state) Example 60 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [[G-1]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl)porphyrin]platinum. Also, Er3+-[[G-1]3-

porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) and Nd3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-1]3-porphyrin (phenyl)3(COO-)platinum] 3 (bipyridine) : #em = 978 nm (AeX = 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 1524 nm (#ex = 442 nm, solid state) Nd3+-[[G-1]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 890,1052, 1323 nm (#ex = 442 nm, solid state) Example 61 : Preparation of Yb3+-[[G-2]3- porphyrin (phen Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [[G-2]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) and Nd3+-[[G-2] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) were prepared in the same manner.

Yb3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) platinum]3(bipyridine) : #em = 978 nm (Aex = 442 nm, solid state) Er3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 1524 nm (#ex = 442 nm, solid state) Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 890,1052, 1323 nm (AeX = 442 nm, solid state) Example 62 : Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4-

carboxyphenyl) porphyrin] platinum. Also, in the same manner, Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) and Nd3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) were prepared.

Yb3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 978 nm (#ex = 442 nm, solid state) Er3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) 1524 nm (#ex = 442 nm, solid state) Nd3+-[[G-3] 3-porphyrin (phenyl) 3 (COO- platinum] 3 (bipyridine) : #em = 890,1052, 1323 nm (#ex = 442 nm, solid state) Example 63 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [[G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) and Nd3+-[EG-4] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) were synthesized in the same manner.

Yb3+-[[G-4]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Xem = 978 nm (#ex = 442 nm, solid state) Er3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 1524 nm (Agx = 442 nm, solid state) Nd3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (bipyridine) : Aem = 890,1052, 1323 nm (#ex = 442 nm, solid state) [Reaction Scheme 76] O. Ln In. O I y w v r W W IGI1I N. N-/N. : : M \-O + _. N i /\/'M KH1BIPY /\ 3 n LnCl3iTHF/EtOH G _N N \ /. Ln, N \ 6 i COOH COOH ol [Gn] M=Zn Mt Pt 01 Cl.

Example 64 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) 3 (terpyridine) (Reaction Scheme 77) The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.

Also, Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) and Nd3+-[[G-1]3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)]3 (terpyridine):#em=978 nm (#ex = 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine): Aem =1428 nm (#ex = 442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : #em=890, 1052,1323 nm (Aex=442nm, solid state) Example 65: Preparation of Yb3+-[[G-2]3- porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) (Reaction Scheme 77) The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.

Also, Er3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) 3 (terpyridine) and Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) were synthesized in the same manner.

Yb3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine): #em=978nm (#ex = 442 nm, solid state)

Er- [ [G-2] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : Aem =1428nm (AeX =442 nm, solid state) Nd3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) =890,1052, 1323nm (#ex=442 nm, solid state) Example66 : PreparationofYb- [ [G-3J3- porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) (Reaction Scheme 77) The title compound was prepared in the same manner as in Example 3 except that terpyridine was used bipyridine. Also, Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) and Nd3+-[[G- 3] 3-porphyrin (phenyl) 3 (COOJ-] 3 (terpyridine) were prepared in the same manner.

Yb- [ [G-3] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : Aem =978nm (#ex= 442 nm, solid state) Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : Aem =1428nm (#ex = 442 nm, solid state) Nd3+-[EG-3] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : #em= 890, 1052, 1323nm (#ex = 442 nm, solid state) Example 67 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) 3 (teryridine) (Reaction Scheme 77) The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.

Also, Er3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) and Nd3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) were prepared in the same manner.

3+- [-) 13 (terpyridine): Aem =978nm (#ex = 442 nm, solid state) Er3+-[[G-4]3-porphyrin (phenyl) 3 (COO-)] 3 (terpyridine) : Aem =1428nm (Ne,, = 442 nm, solid state) Nd34-[[G-4] 3-porphyrin (phenyl) 3(COO-)]3 (terpyridine): #em=890, 1052, 1323nm (#ex = 442 nm, solid state) [Reaction Scheme 77]

l IGnI LGnl. O v,-/ [Gn] N N \ _, H N-p,. N 0/, \/\ KHIBtwy /-\ \, ns___N \ NH N, \/Gn, LnCt3IT ; iFIEtOH [Gn] -N HN \/ "- 3 COOL 0, [Gn] Example 68 : Preparation of Yb3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-1] 3-5,10, 15-triphenyl-20-(4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine and Nd3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : #em = 978 nm (AeX = 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3. (terpyridine) : #em = 1520 nm (#ex = 442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 890,1052, 1323 nm (ex = 442 nm, solid state) Example 69 : Preparation of Yb 3+_ [G-213- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-2]3-5, 10, 15-triphenyl-20- (4-

carboxyphenyl) porphtrin] zinc. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) and Nd3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 978 nm (#ex = 442 nm, solid state) Er3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 1520 nm (Aex = 442 nm, solid state) Nd3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 890,1052, 1323 nm (#ex = 442 nm, solid state) Example 70: Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-3]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) and Nd3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) 978 nm (AeX = 442 nm, solid state) Er3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 1520 nm (AeX = 442 nm, solid state) Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : #em = 890, 1052,1323 nm (Aex = 442 nm, solid state) Example 71 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [ [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+-[[G-4]3-

porphyrin (phenyl) 3 (COO) zinc] 3 (terpyridine) and Nd3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) 978 nm (Aex = 442 nm, solid state) Er3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) : Aem = 1520 nm (Aex = 442 nm, solid state) Nd3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) zinc] 3 (terpyridine) zero 890,1052, 1323 nm (#ex = 442 nm, solid state) Example 72 : Preparation of Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO-)platinum]3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-1]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-1]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) and Nd3+-[[G-1] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : Aem 978 nom 442 nm, solid state) Er3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : Xem = 1524 nm (#ex = 442 nm, solid state) Nd3+-[[G-1] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : #em = 890, 1052, 1323 nm (Aex = 442 nm, solid state) Example 73 : Preparation of Yb3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-2]3-5, 10, 15-triphenyl-20- (4-

carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) and Nd3+-[[G-2]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) platinum]3(terpyridine) : #em ='978 nm (#ex = 442 nm, solid state) Er3+-[[G-2] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : = 1524 nm (Aex = 442 nm, solid state) Nd3+-[[G-2]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : =890, 1052,1323 nm (#ex = 442 nm, solid state) Example 74 : Preparation of Yb3+-[[G-3]3- porphyrin (phenyl) 3(COO-)platinum] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, using [[G-3]3-5, 10, 15-triphenyl-20- (4-' carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-3]3- porphyrin (phenyl) 3 (COO-) platinum]3 (terpyridine) and Nd3+-[[G-3] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) = 978. nm (#ex = 442 nm, solid state) Er3+-[[G-3] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) = 1524 nm (#ex = 442 nm, solid state) Nd3+-[[G-3]3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : Xem = 890, 1052,1323 nm (#ex = 442 nm, solid state) Example 75 : Preparation of Yb3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) (Reaction Scheme 78)

The title compound was prepared in the same manner as in Example 3, using [[G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+-[[G-4]3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) and Nd3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) were prepared in the same manner.

Yb3+-[[G-4] 3-porphyrin (phenyl) 3 (COO) platinum] 3 (terpyridine) : Aem = 978 nm (#ex = 442 nm, solid state) Er3+-[[G-4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : #em = 1524 nm (AeX = 442 nm, solid state) Nd3+- [ [G-'4] 3-porphyrin (phenyl) 3 (COO-) platinum] 3 (terpyridine) : #em = 890, 1052, 1323 nm (#ex = 442 nm, solid state) [Reaction Scheme 78] o. [GnJ N 3 i i ' fV/ Gn \/N'N -KHIBtpY /\/N. : M1. N \-, n3- \ 3 /OGn] LnC1317HF I EtOH [Gn]-N. N \/ . ° COOH M=ZnPt 01 caf.

Example 76: Photoluminescent properties of rare earth complex compounds Ln3+-([NA-1] 2-CO2~) 3 (bipyridine). was added to a polymer material of polymethylmethacrylate at amounts of 3 wt%, 5 wt%, 10 wt%, 15 wt%, 18 wt% and 20 wt% relative to the polymer material. The mixture was dissolved in a chloroform solvent having a weight corresponding to 10 times the weight of the mixture, to prepare a solution. This solution was coated on a quartz substrate by a spin-coating process to form a polymer thin film. The formed thin film was irradiated with a 325-nm

wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths: (1) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of 4F3/2 " In/2 that is the photoluminescent property of ytterbium (Yb) ions; (2) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of I13/2-> 4I15/2 that is the photoluminescent property of erbium (Er) ions; and (3) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2F5/2 -> 4F7/2 that is the photoluminescent property of Nd ions. The results showed that the photoluminescence intensity was increased with an increase in the content of the. complex compound, and when the content of the erbium complex was increased to 15%, the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 40 times increased. Also, it could be found that the polymer thin film doped with the erbium complexes exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions, and thus had high optical amplification effect. Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes.

Example 77: Photoluminescence properties of rare earth complex compounds Ln3+-[LG-2] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) was added to a polymer material of polymethylmethacrylate at amounts of 3 wt%, 5 wt%, 10 wt%, 15 wt%, 18 wt% and 20 wt% relative to the polymer material. The mixture was dissolved in a chloroform solvent having a weight corresponding to 10 times the

weight of the mixture, to prepare a solution. This solution was coated on a quartz substrate by a spin-coating process to form a polymer thin film. The formed thin film was irradiated with a 442-nm wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths: (1) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of 4F3/2-> 4Ill/2 that is the photoluminescent property of ytterbium (Yb) ions; (2) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of 113/2"> Iis/sthat is the photoluminescent property of erbium (Er) ions; and (3) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2F5/2-> 4 F7/2 that is the photoluminescent property of Nd ions. The results showed that the photoluminescence intensity was increased with an increase in the content of the complex compound, and when the content of the erbium complex was increased to 15%, the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 125 times increased. Also, it could be found that the polymer thin film doped with the erbium complex exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions, and thus had high optical amplification effect. Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes.

As a result, it can be found that the rare earth ion- containing porphyrin complexes of the present invention have an excellent light-harvesting effect and an excellent solubility in polymer medium and do not show the aggregation phenomenon and thus interaction between the rare earth metal ions. This suggests that the complexes of the present invention have a very

excellent optical amplification effect. Also, the present invention makes it possible to prepare the rare earth ion- organic ligand complexes whose photophysical properties can be controlled such that light can be amplified at various wavelengths as shown in FIG. 6. Particularly, as apparent from Example 77 and FIGS. 2 to 5, the dendritic complexes have very high photoluminescence intensities at the respective wavelengths.

This indicates that the compounds of the present invention have very excellent optical amplification properties.

Industrial Applicability In the existing method of doping the silica optical fiber with Er3+ ions, the doping concentration of Er3+ was limited to about 100-1,000 ppm. When the concentration exceeds this limit, a non-light-emitting process will generally occur to cause a rapid reduction in optical amplification efficiency. For this reason, it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide- type optical integrated circuits.

Furthermore, many researches on the development of optical amplifier materials comprising an inorganic or organic polymer medium doped with rare earth ions, such as Er3+, or chelate complexes, have been conducted up to now. However, in such prior optical amplifier materials, an effect of high optical amplification cannot be achieved since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals in the polymer medium. Also, if the rare earth metals are used at high doping concentration, the aggregation between the metal ions and also the phase separation

between the rare earth ions and the silica medium will occur to cause a reduction in optical amplification effect.

On the other hand, the present invention makes it possible to solve such problems occurring in the prior art. Namely, the present invention provides the rare earth ion-containing porphyrin complex compounds, which have a light-harvesting effect as shown in FIG. 1, and do not show the aggregation between the rare earth metals and thus the interaction between the rare earth metal ions. Also, as shown in FIG. 5, the dendritic complexes of the present invention have several times higher optical amplification effect than that of the prior material doped with the rare earth ions.

In addition, the present invention makes it possible to prepare the rare earth metal-containing organic ligand complex compounds whose photophysical properties can be controlled by suitable selection of the rare earth metal such that light at various wavelengths can be amplified as shown in FIG. 6.