SUNA EDGARS (LV)
| CN112300121A | 2021-02-02 | |||
| US3674798A | 1972-07-04 | |||
| US0001972A | 1841-02-10 | |||
| US5336441A | 1994-08-09 | |||
| US6604531B2 | 2003-08-12 | |||
| US4719930A | 1988-01-19 | |||
| US4183366A | 1980-01-15 |
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| Claims 1. A compound according to the general formula 1 in which R1 is an aliphatic carbon chain attached to a pyridinium moiety at position 1; R2 is a neutral or electron-rich substituent with Hammett c para constants in the range of 0.90 to 0.23; L is an aromatic linker; X is a negatively charged NCh-, MsO“, CIOC, Cl“ counterion; except where R1 = -Me, L = 1,4-phenylene, R2 = -H, X = C1OC. 2. The compound according to claim 1, wherein R1 is - (CH2)n-CH2R3, where n = 0 to 11, and R3 is a terminal substituent including, -H, -Me, -COO-, -CN, -Ph; R2 is selected from -H, -Me, -/Bu, -Ph, -OMe, -NMe2, -NPI12, -NH2, -OH, -SiMes; L is a 1,4-phenylene, 2,6-naphthalene, 1,4-naphthalene fragment; X is a negatively charged NOs-, MsO“, CIOC, Cl“ counterion; except where R1 = -Me, L = 1,4-phenylene, R2 = -H, X = C1OC. 3. Process for the synthesis of a compound of formula 1 according to claim 1 or 2 wherein R1 is an aliphatic carbon chain attached to a pyridinium moiety at position 1; R2 is a neutral or electron-rich substituent with Hammett c para constants in the range of 0.90 to 0.23; L is an aromatic linker; X is a negatively charged NCh-, MsO“, ClOY, Cl“ counterion; with the proviso except where R1 = -Me, L = 1,4-phenylene, R2 = -H, X = CIOC; comprises alkylation of a compound of formula 3 with Rx-Y in MeCN solution, where Y is Cl, Br, I, OMs, OTs, OTf and counterion metathesis of the resulting compound of formula 2 with HX or AgX. 4. The compound according to claim 1 or 2 for use in light emitting electrochemical cell (LEC) devices. |
TECHNICAL FIELD
[001] The present invention relates to light emitting pyridinium salts and synthesis thereof. The present invention also relates to the application of the light emitting pyridinium salts.
BACKGROUND ART
[002] Pyridinium moiety is a cationic aromatic fragment balanced with an anion. Accordingly, a compounds where both an anion and a pyridinium cation is present is called pyridinium salts. The anion of pyridinium salt is generally a separate molecule, however pyridinium salts can form a zwitterionic species as well. The most common strategy to obtain pyridinium salts is the alkylation of a pyridine ring.
[003] Alkylated pyridinium salts have found widespread applications as electrolytes [1], surfactants in the separation of minerals [2], dry cleaning additives [3], corrosion inhibitors [4], additives for cosmetics [5], anti-fouling and anti-microbial agents [6], anti-malarial substances [7] and many others [8],
[004] Pyridinium salts have also found application as luminescent molecules and sensors. In 2010 Fossey found application for pyridinium salts as alkylating reagent sensors [9] in solution, owing the luminescent response to the formation of it- it + interactions.
[005] In 2014 Zhang reported a pyridinium salt that displays white emission [10], The white emission resulted from the formation of an additional charge transfer emission band in the solid state.
[006] The charge transfer type emission through the use of it- it + interactions were used to obtain pyridinium luminophores with high solid state emission by Suna in 2019 [11],
[007] In 2020 Suna also reported that the use of perchlorate anion in pyridinium salts facilitates the highest solid state emission among various anion choices [12],
[008] Pyridinium salts are conductive materials [1], and thus are compatible with the emissive layers of light emitting electrochemical cells (LECs) [13], However pyridinium salts are underutilized in LEC devices.
[009] In 2022 Su reported orange-red LEC device with a pyridinium luminophore as an emitter [14], The pyridinium ring featured substitution at positions 1, 2 and 4.
The present invention [010] During atempts to widen the scope of the underutilized pyridinium luminophores we surprisingly have found that a variety of pyridinium salts display outstanding solid state emission properties. Hence, these materials can be used in solid state emitting devices, for example in light emitting electrochemical cells (LECs).
[Oi l] The objects of the present invention are pyridinium salts with the general formula 1.
Detailed description of the invention
[012] We disclose pyridinium salts with the general formula 1: wherein
R 1 is an aliphatic carbon chain bonded to the pyridinium moiety at position 1. The term ‘ ’aliphatic carbon chain” refers to a stright or branched hydrocarbon chain containing between 1 and 12 carbon atoms with an optional terminal substituent. Terminal substituent refers to a substituent attached at the end of the aliphatic carbon chain. For example -(CHijn-CHiR 3 , where n = 0 to 11, and R 3 is a terminal substituent that include but are not limited to, -H, -Me, -COO-, -CN, -Ph;
R 2 is a neutral or electron donating substituent that complements the carbazole core. The term ‘’neutral or electron rich substituent” refers to a substituent that is caractarized by Hammett o pa ra constants in the range between -0.90 and 0.23. Such as -H, -Me, -/Bu, -Ph, -OMe, -NMe2, -NPh2, -NH2, -OH, -SiMe? or alternatively the carbazole can be replaced with a larger condensed moiety. The term ’’larger condensed moiety” refers to a dibenzo [a, g] carbazole, dibenzo[b,g]carbazole, dibenzo[c,g]carbazole, dibenzo[a,h]carbazole, dibenzo[b,h] carbazole, dibenzo[c,h] carbazole, dibenzo[a,i]carbazole, dibenzo[b,i]carbazole or dibenzo[c,i]carbazole.
L is an aromatic linker. The term ‘’aromatic linker” refers to a disubstituted aromatic moiety that contains a carbazole moiety at one position and a pyridinium moiety at the other. Such as 1,4- phenylene, 2,6-naphtalene, 1,4-naphtalene;
X is a negatively charged counter ion, such as NO3-, MsO-, CIO4-, Cl-.
With the proviso except when R 1 = -Me, L = 1 ,4-phenylene, R 2 = -H, X = CIO4-. [013] Synthesis of pyridinium luminophores follow the general Scheme 1: wherein the building blocks 4 in a Suzuki-Miyaura reaction with pyridine 4-boronic acid affords compounds with general formula 3.
[014] Alternatively bromides 9, 10, 11 in a Suzuki-Miyaura reaction with pyridine 4-boronic acid gives halogenides 5, 6 and 7. Subsequent Ullmann coupling for compounds 6 and 7, or S\Ar reaction for compound 5, with 3,6-disubstituted carbazoles 8 form compounds with general formula 3.
[015] Pyridines with general formula 3 were alkylated with i -Y where Y is selected from Cl, Br, I, OMs, OTs, OTf in MeCN to form pyridinium salts 2. Optionally the formed counter ion Y“ (for example I-) in compounds 2 was exchanged to X“ to form pyridinium salts 1, through the use of reversed phase column chromatography with HX added to the eluent or by the use of AgX salts, thus performing counterion metathesis.
[016] For example 1.00 equivalents of the commercially available 9-(4-bromophenyl)-977- carbazole 4a, 1.05 equivalents of pyridine 4-boronic acid, 0.05 equivalents of Pd(dppf)x2CH2Ch and 3.0 equivalents of K2CO3 in a refluxing MeCNiFFO - 6: 1 mixture reacted to afford 9-(4- (pyridin-4-yl)phenyl)-9H-carbazole 3a in a 75% yield after purification with column chromatography. [017] Compound 3a was alkylated with BuBr in MeCN to afford the pyridinium bromide 2b, which after treatment with AgClC afforded the pyridinium perchlorate lb in an 86% yield after two steps.
Compound lb: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.08-9.03 (2H, m), 8.57-8.52 (2H, m), 8.36- 8.31 (2H, m), 8.28-8.23 (2H, m), 7.95-7.90 (2H, m), 7.55-7.44 (4H, m), 7.37-7.30 (2H, m), 4.59 (2H, t, J 7.2 Hz), 1.99-1.88 (2H, m), 1.39-1.28 (2H, m), 0.93 (3H, t, =7.2 Hz) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 154.2, 145.1, 140.7, 139.9, 132.4, 130.4, 127.6, 127.0, 124.9, 123.5, 121.2, 121.1, 110.1, 60.3, 32.9, 19.2, 13.7 ppm.
[018] In the alternative route 1.00 equivalents of commercially available 1,4-dibromobenzene 10, 1.00 equivalents of pyridine 4-boronic acid, 0.05 equivalents of Pdidppf CHoCb and 3.0 equivalents of K2CO3 in a refluxing MeCNitbO - 6: 1 mixture reacted to afford 4-(4- bromophenyl)pyridine 6 in a 38% yield after purification with column chromatography. Compound 6 in an Cul/L-Proline catalyzed Ullmann type reaction in the presence of K2CO3 formed pyridine 3c in an 79% yield after purification with column chromatography. Subsequent alkylation with Mel and ion exchange with AgClC resulted in pyridinium salts 2c and lc respectively, with an overall yield of 75% over two steps.
Compound lc: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 8.99-8.94 (2H, m), 8.75-8.70 (2H, m), 8.56- 8.51 (2H, m), 8.38-8.32 (2H, m), 8.00-7.95 (2H, m), 7.85-7.79 (6H, m), 7.63-7.59 (2H, m), 7.53- 7.47 (4H, m), 7.39-7.32 (2H, m), 4.35 (3H, s) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 153.8, 145.9, 140.8, 140.5, 139.9, 133.6, 132.5, 129.4, 127.4, 127.3, 127.1, 126.0, 124.5, 124.4, 119.4, 110.8, 47.6 ppm.
[019] Alternatively compound 3c was alkylated with BuBr in MeCN to afford the pyridinium bromide 2d, which after treatment with AgClCU afforded the pyridinium perchlorate Id in a 70% yield after two steps. Compound Id: 'H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.09-9.02 (2H, m), 8.75- 8.70 (2H, m), 8.56-8.51 (2H, m), 8.38-8.32 (2H, m), 7.99-7.91 (2H, m), 7.85-7.77 (6H, m), 7.63- 7.57 (2H, m), 7.53-7.46 (4H, m), 7.39-7.32 (2H, m), 4.58 (2H, t, J=7.4 Hz), 1.94 (2H, quintet, J=7.4 Hz), 1.34 (2H, sextet, J=7.4 Hz), 0.94 (3H, t, =7.4 Hz) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 154.1, 145.0, 140.8, 140.5, 139.8, 133.6, 132.4, 130.5, 129.4, 127.4, 127.3, 127.1, 126.0, 124.9, 124.5, 119.4, 110.8, 60.3, 32.9, 19.2, 13.7 ppm.
3c 2d 1d
[020] Using the previously described routes other compounds were synthesized. For example, compounds le, If, lg, lh, li etc.
Compound le: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.07-9.02 (2H, m), 8.56-8.51 (2H, m), 8.36- 8.27 (4H, m), 7.93-7.87 (2H, m), 7.54-7.49 (2H, m), 7.48-7.43 (2H, m), 4.58 (2H, t, J=7.4 Hz), 1.98-1.89 (2H, m), 1.40 (18H, s), 1.39-1.28 (2H, m), 0.93 (3H, t, J=7.4 Hz) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 154.2, 145.0, 143.8, 141.2, 138.2, 131.8, 130.4, 127.0, 124.8, 124.4, 123.7, 117.2, 109.7, 60.3, 34.9, 32.9, 32.1, 19.2, 13.7 ppm. Compound If: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 8.97-8.92 (2H, m), 8.54-8.50 (2H, m), 8.34- 8.28 (4H, m), 7.93-7.87 (2H, m), 7.54-7.49 (2H, m), 7.48-7.43 (2H, m), 4.33 (3H, s), 1.40 (18H, s) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 153.8, 145.9, 143.8, 141.2, 138.2, 131.8, 130.3, 127.0, 124.4, 123.7, 117.2, 109.7, 47.5, 34.9, 32.1 ppm.
Compound lg: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.10-9.06 (2H, m), 8.42-8.38 (2H, m), 8.34- 8.30 (2H, m), 8.03-7.98 (1H, m), 7.97-7.90 (2H, m), 7.72-7.66 (1H, m), 7.55-7.49 (1H, m), 7.42- 7.36 (2H, m), 7.35-7.30 (2H, m), 7.18-7.14 (1H, m), 6.98-6.93 (2H, m), 4.44 (3H, s) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 155.6, 145.8, 141.8, 135.8, 135.2, 131.4, 130.7, 129.0, 128.9,
128.8, 128.4, 126.8, 125.8, 123.7, 123.1, 121.1, 120.7, 110.1, 48.0 ppm.
Compound lh: 'H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.13-9.07 (2H, m), 9.01-8.96 (2H, m), 8.57- 8.52 (2H, m), 8.40-8.34 (2H, m), 8.16-8.11 (2H, m), 8.02-7.97 (2H, m), 7.96-7.92 (2H, m), 7.80- 7.73 (2H, m), 7.67-7.62 (2H, m), 7.61-7.55 (2H, m), 4.36 (3H, s) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 153.8, 146.0, 139.5, 137.4, 133.8, 130.4, 130.3, 129.7, 129.2, 128.6, 127.8, 126.4, 124.8, 124.7, 124.3, 117.3, 112.0, 47.6 ppm.
Compound li: ’H NMR (400 MHz, (CD 3 ) 2 SO, 5): 9.00-8.94 (2H, m), 8.86-8.82 (1H, m), 8.63- 8.57 (2H, m), 8.40-8.36 (1H, m), 8.33-8.24 (4H, m), 8.22-8.17 (1H, m), 7.90-7.84 (1H, m), 7.53- 7.43 (4H, m), 7.36-7.30 (2H, m), 4.35 (3H, s) ppm.
13 C NMR (101 MHz, (CD 3 ) 2 SO, 5): 154.4, 145.9, 140.3, 137.0, 135.4, 132.0, 131.8, 131.6, 129.9,
129.2, 126.9, 126.4, 125.4, 124.7, 124.6, 123.4, 121.0, 120.9, 110.1, 47.5 ppm. References:
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