HAYOZ PASCAL (CH)
CHEN HU (SA)
MCCULLOCH IAIN (GB)
KING ABDULLAH UNIV OF SCIENCE & TECHNOLOGY (SA)
| WO2018104367A2 | 2018-06-14 |
| GB2472413A | 2011-02-09 |
CAI, ZHENGXU ET AL: "Synthesis of Alternating Donor-Acceptor Ladder-Type Molecules and Investigation of Their Multiple Charge-Transfer Pathways", ANGEWANDTE CHEMIE, INTERNATIONAL EDITION, vol. 57, no. 22, 8 March 2018 (2018-03-08), pages 6442 - 6448, XP002789823, ISSN: 1433-7851, DOI: 10.1002/ANIE.201713323
CAI, ZHENGXU ET AL: "Exceptional single-molecule transport properties of ladder-type heteroacene molecular wires", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 138, no. 33, 4 August 2016 (2016-08-04), pages 10630 - 10635, XP002789824, ISSN: 0002-7863, DOI: 10.1021/JACS.6B05983
ZHENG, TIANYUE ET AL: "Roles of Quinoidal Character and Regioregularity in Determining the Optoelectronic and Photovoltaic Properties of Conjugated Copolymers", MACROMOLECULES, vol. 47, no. 18, 23 September 2014 (2014-09-23), WASHINGTON, DC, UNITED STATES, pages 6252 - 6259, XP002789825, ISSN: 0024-9297, DOI: 10.1021/MA501152V
W. ZHANGJ. SMITHS. E. WATKINSR. GYSELM. MCGEHEEA. SALLEOJ. KIRKPATRICKS. ASHRAFT. ANTHOPOULOSM. HEENEY, J. AM. CHEM. SOC., vol. 132, 2010, pages 11437
| Claims 1. Com pou nds comprising at least one unit of formu la wherein M l and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system; X is at each occurrence O, S, Se or Te, Q is at each occurrence C, Si or Ge, R1 is at each occurrence selected from the grou p consisting of H, Ci-50-alkyl, - [CH2]0- [0- SiRaRa]p-OSiRaRaRa, - [CH2]0- [RaRaSi-0]p-SiRaRaRa, - [CRbRb]q-CRbRbRb, C2-50-alkenyl, C2-50- alkynyl, C5-8-cycloalkyl, C6-14-aryl and 5 to 14 membered heteroaryl, wherein o is an integer from 0 to 10, p is an integer from 1 to 40, Ra is at each occu rrence C^^-alkyl, C2_i0-alkenyl or C2-i0-alkynyl, q is an integer from 1 to 50, Rb is at each occurrence H or halogen, with the provisio that not all Rb in - [CRbRb]q- CRbRbRb are H, Ci-so-alkyl, C2-50-alkenyl and C2-50-a I kyny I can be substituted with one to fou r substitu ents independently selected from the group consisting of ORc, OC(0)-Rc, C(0)-ORc, C5-8-cycloalkyl can be substituted with one or two substituents independently selected from the grou p consisting of C^^-alkyl, C2-10-alkenyl, C2-10-alkynyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, N RCRC, N Rc-C(0) Rc, C(0)-N RcRc, N [C(0) Rc] [C(0) Rc], SRC, halogen, CN, -SiRcRcRc and N02; and one CH2-group of C5-8-cycloalkyl can be replaced by O, S, OC(O), CO, N RC or N Rc-CO, Cg- -a ry I and 5 to 14 membered heteroaryl can be substituted with one to th ree sub stituents independently selected from the grou p consisting of C^^-alkyl, C2-10-a I kenyl, nyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, N RCRC, N Rc-C(0) Rc, C(0)-N RcRc, ] [C(0) Rc], SRC, halogen, CN, and N02, wherein Rc is at each occu rrence H, C^Q-alkyl, C2-10-alkenyl or C2-10-a I kyny I, R2 is at each occu rrence H, C^Q-alkyl, C2-30-alkenyl or C2-30-a I kyny I or halogen, n is 0, 1, 2, 3 or 4, m is 0, 1, 2, 3 or 4 Lb and L2 are independently from each other and at each occurrence selected from the grou p consisting of C6-26-arylene, 5 to 20 membered heteroarylene, wherein C6.26-arylene and 5 to 20 membered heteroarylene can be substituted with one to fou r substituents Rd at each occu rrence selected from the grou p consisting of H, C1-30-alkyl, C2-30-alkenyl, C2-30-a I kyny I and halogen, and can be substituted with one or two substituents at each occurrence selected from the grou p consisting of Re, COORe and CN, wherein Re is at each occu rrence selected from the group consisting of H, Ci-30-alkyl, C2-3o-alkenyl and C2-30- alkynyl. 2. The compou nds of claim 1 comprising at least one u nit of formu la ĭ71 wherein X, Q, R1, R2, L1, L2, n and m are as defined in claim 1, Y is at each occurrence 0, S, Se or Te, and R3 is at each occurrence H, Ci-30-alkyl, C2-3o-alkenyl or C2-30-a I ky ny I or halogen. 3. The compounds of claim 1 or 2, wherein the compound is a polymer. 4. The compounds of any of claims 1 to 3, wherein X is O, S or Se. 5. The compounds of any of claims 1 to 4, wherein Q is C or Si. 6. The compounds of any of claims 1 to 5, wherein R1 is at each occurrence selected from the group consisting of H, Ci-50-alkyl, -[CH2]0-[RaRaSi-0]p-SiRaRaRa, -[CRbRb]q- CRbRbRb, C2-50-alkenyl and C2-50-alkynyl, wherein o is an integer from 1 to 10, p is an integer from 1 to 40, Ra is at each occurrence C^^-alkyl, C2-10-alkenyl or C2-10-alkynyl, q is an integer from 1 to 50, Rb is at each occurrence H or halogen, with the provisio that not all Rb in -[CRbRb]q- CRbRbRb are H, Ci-so-alkyl, C2-50-alkenyl and C2-50-a I kyny I can be substituted with one to four substitu ents independently selected from the group consisting of ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, N [C(0)Rc] [C(0)Rc], SRC, CN, and N02, wherein Rc is at each occurrence H, Ci-20-alkyl, C2-10-alkenyl or C2-10-alkynyl. 7. The compounds of any of claims 1 to 5, wherein R1 is at each occurrence Ci-50-alkyl. 8. The compounds of any of claims 1 to 7, wherein R2 is at each occurrence H, Ci-30-alkyl or halogen. 9. The compounds of any of claims 1 to 8, wherein m is 0, 1 or 2. 10. The compounds of any of claims 1 to 9, wherein n is 0. 11. The compounds of any of claims 1 to 10, wherein L1 and L2 are independently from each other and at each occurrence selected from the group consisting of C6-26-arylene, 5 to 20 membered heteroarylene, and wherein C6.26-arylene and 5 to 20 membered heteroarylene can be substituted with one to four substituents Rd at each occurrence selected from the group consisting of Ci-30-alkyl, C2-30-alkenyl, C2-30-a I ky ny I and halogen, wherein C6-26-arylene, optionally substituted with one to four substituents Rd, is selected from the group consisting of wherein R101 is at each occu rrence H or Ci-30-alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to fou r substi- tutents Rd, are selected from the grou p consisting of wherein R103 is at each occurrence H, Ci-30-alkyl, C2-3o-alkenyl or C2-30-a I ky ny I or halogen, R102 is at each occurrence H or C1-30-a I ky I. 12. A process for the preparation of the compounds of claim 1 comprising at least one unit of formula Wherein Ml and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system; X is at each occurrence 0, S, Se or Te, Q is at each occurrence C, Si or Ge, R1 is at each occurrence selected from the group consisting of H, Ci-50-alkyl, -[CH2]0-[0- SiRaRa]p-OSiRaRaRa, -[CH2]0-[RaRaSi-0]p-SiRaRaRa, -[CRbRb]q-CRbRbRb, C2-50-alkenyl, C2-50- alkynyl, C5-8-cycloalkyl, C6-14-aryl and 5 to 14 membered heteroaryl, wherein o is an integer from 0 to 10, p is an integer from 1 to 40, Ra is at each occurrence Ci_i0-alkyl, C2-10-alkenyl or C2-10-alkynyl, q is an integer from 1 to 50, Rb is at each occurrence H or halogen, with the provisio that not all Rb in -[CRbRb]q- CRbRbRb are H, Ci-so-alkyl, C2-50-alkenyl and C2-50-a I kyny I can be substituted with one to four substitu ents independently selected from the group consisting of ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, N[C(0)Rc][C(0)Rc], SRC, CN, -SiRcRcRcand N02, C5-8-cycloalkyl can be substituted with one or two substituents independently selected from the group consisting of Ci_i0-a I kyl, C2-10-alkenyl, C2-10-alkynyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, N[C(0)Rc][C(0)Rc], SRC, halogen, CN, -SiRcRcRc and N02; and one CH2-group of C5-8-cycloalkyl can be replaced by O, S, OC(O), CO, NRC or NRc-CO, Cg- -a ry I and 5 to 14 membered heteroaryl can be substituted with one to three sub stituents independently selected from the group consisting of Ci_i0-a I kyl, C2-10-alkenyl, nyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, ] [C(0)Rc], SRC, halogen, CN, and N02, wherein Rc is at each occurrence H, Ci-20-a I kyl, C2-10-alkenyl or C2-10-alkynyl, R2 is at each occurrence H, Ci-30-alkyl, C2-30-alkenyl or C2-30-a I kyny I or halogen, n is 0, 1, 2, 3 or 4, m is 0, 1, 2, 3 or 4 U and L2 are independently from each other and at each occurrence selected from the group consisting of C6-26-arylene, 5 to 20 membered heteroarylene, wherein C6.26-arylene and 5 to 20 membered heteroarylene can be substituted with one to four substituents Rd at each occurrence selected from the group consisting of H, Ci-30-alkyl, C2-30-alkenyl, C2-30-a I kyny I and halogen, and can be substituted with one or two substituents at each occurrence selected from the group consisting of Re, COORe and CN, wherein Re is at each occurrence selected from the group consisting of H, Ci-30-alkyl, C2-3o-alkenyl and C2-30-a I ky ny I, which process comprises the step of treating a compound of formula or wherein Ml, M2, X, Q, R1 and R2 are as defined for units of formul 1 and 1’, with acid to afford a compound of formula wherein Ml, M2, X, Q, R1 and R2 are as defined for the units of formula 1 and 1’. 13. Compou nds of formu la wherein M l and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system; X is at each occu rrence O, S, Se or Te, Q is at each occurrence C, Si or Ge, R1 is at each occurrence selected from the grou p consisting of H, Ci-50-alkyl, - [CH2]0- [0- SiRaRa]p-OSiRaRaRa, - [CH2]0- [RaRaSi-0]p-SiRaRaRa, - [CRbRb]q-CRbRbRb, C2-50-alkenyl, C2-50- alkynyl, C5-8-cycloalkyl, C6-14-aryl and 5 to 14 membered heteroaryl, wherein o is an integer from 0 to 10, p is an integer from 1 to 40, Ra is at each occurrence C^^-alkyl, C2_i0-alkenyl or C2-i0-alkynyl, q is an integer from 1 to 50, Rb is at each occurrence H or halogen, with the provisio that not all Rb in -[CRbRb]q- CRbRbRb are H, Ci-so-alkyl, C2-50-alkenyl and C2-50-a I kyny I can be substituted with one to four substitu ents independently selected from the group consisting of ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, N[C(0)Rc][C(0)Rc], SRC, CN, SiRcRcRcand N02, C5-8-cycloalkyl can be substituted with one or two substituents independently selected from the group consisting of Ci_i0-a I kyl, C2-10-alkenyl, C2-10-alkynyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, N[C(0)Rc][C(0)Rc], SRC, halogen, CN, SiRcRcRc and N02; and one CH2-group of C5-8-cycloalkyl can be replaced by O, S, OC(O), CO, NRC or NRc-CO, Cg- -a ry I and 5 to 14 membered heteroaryl can be substituted with one to three sub stituents independently selected from the group consisting of Ci_i0-a I kyl, C2-10-a I kenyl, nyl, ORc, OC(0)-Rc, C(0)-ORc, C(0)-Rc, NRCRC, NRc-C(0)Rc, C(0)-NRcRc, ] [C(0)Rc], SRC, halogen, CN, and N02, wherein Rc is at each occurrence H, C^Q-alkyl, C2-10-alkenyl or C2-10-a I kyny I, R2 is at each occurrence H, Ci-30-alkyl, C2-30-alkenyl or C2-30-a I kyny I or halogen. 14. Compounds of claim 13 which are of formula 3A 10 3 Ά 3’D wherein X, Q, R1 and R2 are as defined in claim 13, and Y is at each occurrence 0, S, Se or Te, and R3 is at each occurrence H, Ci-30-alkyl, C2-3o-alkenyl or C2-30-a I ky ny I or halogen. 15. An electronic device comprising the compounds of any of claims 1 to 11. 16. The electronic device of claim 15, wherein the device is an organic field effect transis tor. 17. Use of the compounds of any of claims 1 to 11 as semiconducting material. |
The present invention relates to compounds, including polymers, a process for the prepara tion of these compounds, to intermediates of the process, to electronic devices comprising these compounds, as well as to the use of these compounds as semiconducting material.
Organic semiconducting materials can be used in electronic devices such as organic photo voltaic devices (OPVs), organic field-effect transistors (OFETs), organic light emitting di odes (OLEDs), organic photodiodes (OPDs) and organic electrochromic devices (ECDs).
It is desirable that the organic semiconducting materials are compatible with liquid pro cessing techniques such as spin coating as liquid processing techniques are convenient from the point of processability, and thus allow the production of low cost organic semicon ducting material-based electronic devices. I n addition, liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and me chanically flexible organic semiconducting material-based electronic devices.
For application in organic photovoltaic devices (OPVs), organic field-effect transistors (OFETs), and organic photodiodes (OPDs), it is further desirable that the organic semicon ducting materials show high charge carrier mobility and are of high stability under ambient conditions.
It was the object of the present invention to provide new and improved organic semicon ducting materials.
This object is solved by the compounds of claim 1, the process of claim 12, the intermedi ates of claim 13, the electronic device of claim 15 and the use of the compounds of claim 17.
The compounds of the present invention comprise at least one unit of formula
or
wherein
Ml and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system;
X is at each occurrence 0, S, Se or Te,
Q is at each occurrence C, Si or Ge,
R 1 is at each occurrence selected from the group consisting of H, Ci -50 -alkyl, -[CH 2 ] 0 -[0- SiR a R a ] p -OSiR a R a R a , -[CH 2 ] 0 -[R a R a Si-0] p -SiR a R a R a , -[CR b R b ] q -CR b R b R b , C 2-50 -alkenyl, C 2-50 - alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl and 5 to 14 membered heteroaryl, wherein
o is an integer from 0 to 10,
p is an integer from 1 to 40,
R a is at each occurrence Ci_i 0 -alkyl, C 2-10 -alkenyl or C 2-10 -alkynyl,
q is an integer from 1 to 50,
R b is at each occurrence H or halogen, with the provisio that not all R b in -[CR b R b ] q - CR b R b R b are H,
Ci-so-alkyl, C 2-50 -alkenyl and C 2-50 -a I ky ny I can be substituted with one to four substitu ents independently selected from the group consisting of OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , NR C R C , NR c -C(0)R c , C(0)-NR c R c , N[C(0)R c ][C(0)R c ], SR C , CN, -SiR c R c R c and N0 2 ,
C 5-8 -cycloalkyl can be substituted with one or two substituents independently selected from the group consisting of Ci_i 0 -a I kyl, C 2-10 -alkenyl, C 2-10 -alkynyl, OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , NR C R C , NR c -C(0)R c , C(0)-NR c R c , N[C(0)R c ][C(0)R c ], SR C , halogen, CN, -SiR c R c R c and N0 2 ; and one CH 2 -group of C 5-8 -cycloalkyl can be replaced by O, S, OC(O), CO, NR C or NR c -CO,
Cg- -a ry I and 5 to 14 membered heteroaryl can be substituted with one to three sub stituents independently selected from the group consisting of Ci_i 0 -a I kyl, C 2-10 -alkenyl, C 2-10 -alkynyl, OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , N R C R C , N R c -C(0) R c , C(0)-N R c R c , N [C(0) R c ] [C(0) R c ], SR C , halogen, CN, and N0 2 , wherein
R c is at each occurrence H, Ci -20 -alkyl, C 2-10 -alkenyl or C 2-10 -alkynyl,
R 2 is at each occu rrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, n is 0, 1, 2, 3 or 4,
m is 0, 1, 2, 3 or 4, and
U and L 2 are independently from each other and at each occu rrence selected from the group consisting of C 6-26 -arylene, 5 to 20 membered heteroarylene, wherein
C 6.26 -arylene and 5 to 20 membered heteroarylene can be substituted with one to fou r substituents R d at each occu rrence selected from the group consisting of H, Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, and can be substituted with one or two substituents at each occurrence selected from the group consisting of R e , COOR e and CN, wherein R e is at each occu rrence selected from the grou p consisting of H, Ci -30 -a I ky I, C 2-30 -alkenyl and C 2-30 -a I ky ny I.
Ci-io-a I ky I, Ci -20 -a I ky I, Ci -30 -a I ky I and C j. so-alkyl can be branched or unbranched. Examples of Ci-io-a I ky I are methyl, ethyl, /7-propyl, isopropyl, /7-butyl, sec-butyl, isobutyl, tert- butyl, n- pentyl, neopentyl, isopentyl, /7-(l-ethyl) propyl, /7-hexyl, /7-heptyl, /7-octyl, /7-(2-ethyl) hexyl, /7-nonyl and /7-decyl. Examples of Ci -20 -a I kyl are Ci_i 0 -a I ky I and /7-undecyl, /7-dodecyl, n- undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, /7-hexadecyl, /7-heptadecyl, n- octadecyl, /7-nonadecyl and /7-icosyl (C 20 ). Examples of Ci -30 -a I kyl and Ci -50 -a I kyl are Ci -20 - alkyl and /7-docosyl (C 22 ), /7-tetracosyl (C 24 ), /7-hexacosyl (C 26 ), /7-octacosyl (C 28 ) and n- triacontyl (C 30 ). C 2-i0 -alkenyl, C 2-2 o-alkenyl, C 2-30 -alkenyl and C 2-50 -alkenyl can be branched or unbranched. Examples of Ci -20 -alkenyl are vinyl, propenyl, c/s-2-butenyl, trans-2-bu\e \, 3-butenyl, cis- 2-pentenyl, / 5/75-2-pentenyl, c/s-3-pentenyl, /A9/7s-3-pentenyl, 4-pentenyl, 2-methyl-3- butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl. Exam ples of C 2-20 -alkenyl are C 2-10 - alkenyl and linoleyl (C 18 ), linolenyl (C 18 ), oleyl (C 18 ), and arachidonyl (C 20 ). Examples of C 2-50 - alkenyl are C 2-20 -alkenyl and erucyl (C 22 ).
C 2-i0 -a I ky ny I, C 2-20 -a I ky ny I and C 2-50 -a I kyny I can be branched or unbranched. Exam ples of C 2 _ 10 -a I ky ny I are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl. Exam ples of C 2-20 -a I kyny I and C 2-50 a I kyny I are u ndecynyl, dodecynyl, u ndecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C 20 ).
Examples of C 5-8 -cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Halogen can be F, Cl, Br and I.
Cg- -a ry I is a 6 to 14 membered monocyclic or polycyclic, such as dicyclic, tricyclic, ring sys tem, wherein the rings are either condensed to each other or connected via a double bond, which C 6-14 -a ry I com prises at least one C-aromatic ring, and which C 6-14 -a ry I may also com prise non-aromatic rings, which non-aromatic rings may com prise heteroatoms such as O,
S, Se, Te, Si, N and Ge, and which C-aromatic rings or non-aromatic ring may be substitut ed, for exam ple by C 1-30 -alkyl, =0, =C(C 1-30 -alkyl) 2 or =C(CN) 2 .
Examples of C 6-14 -a ry I are
5 to 14 membered heteroaryl is a 5 to 14 membered monocyclic or polycyclic, such as di- cyclic, tricyclic or tetracyclic, ring system, wherein the rings are either condensed to each other or connected via a double bond, which 5 to 14 membered heteroaryl comprises at least one heteroaromatic ring having at least one hetroatom selected from the group con sisting of 0, S, Se, N and Te, and which 5 to 14 membered heteroaryl may also comprise aromatic carbon rings or non-aromatic rings, which non-aromatic ring may comprise het eroatoms such as 0, S, Se, Te, Si, N and Ge, and which heteroaromatic rings, aromatic car- bon rings or non-aromatic rings may be substituted, for example by Ci -30 -a I kyl, =0, =C(C 1-30 - a I ky l) 2 or =C(CN) 2 .
Examples of 5 to 14 membered heteroaryl are
.104
10
wherein
R 105 is at each occu rrence H, C^ Q -alkyl, C 2-30 -alkenyl or C 2-30 -a I ky ny I or halogen,
R 104 is at each occu rrence H or C^ Q -alkyl.
C 6-26 -a r yle n e is a 6 to 26 membered monocyclic or polycyclic, such as dicyclic, tricyclic, tet racyclic, pentacyclic or hexacyclic ring system, wherein the rings are either condensed to each other or con nected via a double bond, which C 6-26 -arylene com prises at least one C- aromatic ring, and which C 6-26 -arylene may also com prise non-aromatic rings, which non aromatic rings may com prise heteroatoms such as 0, S, Se, Te, Si, N and Ge, and which C- aromatic rings or non-aromatic ring may be substituted, for exam ple by C^ Q -alkyl, =0, =C(C 1-30 -alkyl) 2 or =C(CN) 2 .
Examples of C 6-26 -arylene are
- I Q -
wherein
R 100 is at each occurrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I kyny I or halogen,
R 101 is at each occurrence H or Ci -30 -alkyl.
5 to 20 membered heteroarylene is a 5 to 20 membered monocyclic or polycyclic, such as dicyclic, tricyclic, tetracyclic, pentacyclic or hexacyclic ring system, wherein the rings are either condensed to each other or connected via a double bond, which 5 to 20 membered heteroarylene comprises at least one heteroaromatic ring having at least one heteroatom selected from the group consisting of O, S, Se, N and Te, and which 5 to 20 membered het eroarylene may also comprise aromatic carbon rings or non-aromatic rings, which non aromatic ring may comprise heteroatoms such as O, S, Se, Te, Si, N and Ge, and which het- eroaromatic rings, aromatic carbon rings or non-aromatic rings may be substituted, for ex ample by Ci -30 -alkyl, =0, =C(C 1-30 -alkyl) 2 or =C(CN) 2 .
Examples of 5 to 20 membered heteroarylene are
10
wherein
R 103 is at each occurrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occurrence H or Ci -30 -a I ky I.
Preferred compounds of the present invention comprise at least one unit of formula
wherein
X, Q, R 1 , R 2 , L 1 , L 2 , n and m are as defined above, and
Y is at each occurrence 0, S, Se or Te, and
R 3 is at each occurrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen.
More preferred compounds of the present invention comprise at least one unit of formula
1A, IB, 1C, ID, l’A, l’B or l’C.
Even more preferred compounds of the present invention comprise at least one unit of for mula 1A, IB, 1C or ID.
Most preferred compounds of the present invention comprise at least one unit of formula
1A.
The compounds of the present invention can be small molecules or polymers. The compounds of the present invention which are small molecules preferably comprise one or two units of formula 1 or 1’ as defined above.
Small molecules have preferably a weight average molecular weight (M w ) of below 1 kDa, more preferably of below 800 Da, and a number average molecular weight (M n ) of below lkDa, more preferably of below 800 Da.
Preferably, the compounds of the present invention are polymers.
The compounds of the present invention which are polymers preferably comprise at least three units of formula 1 or 1’ as defined above.
The polymers have preferably a weight average molecular weight (M w ) of 1 to 10000 kDa and a number average molecular weight (M n ) of 1 to 10000 kDa. The polymers of the pre sent invention have more preferably a weight average molecular weight (M w ) of 1 to 1000 kDa and a number average molecular weight (M n ) of 1 to 100 kDa. The polymers of the pre sent invention have even more preferably a weight average molecular weight (M w ) of 5 to 1000 kDa and a number average molecular weight (M n ) of 5 to 100 kDa. The polymers of the present invention have still more preferably a weight average molecular weight (M w ) of 10 to 1000 kDa and a number average molecular weight (M n ) of 10 to 100 kDa. The polymers of the present invention have most preferably a weight average molecular weight (M w ) of 10 to 100 kDa and a number average molecular weight (M n ) of 5 to 60 kDa. The weight average molecular weight (M w ) and the number average molecular weight (M n ) can be determined by gel permeation chromatography (GPC) e.g. at 80 ° C using chlorobenzene or preferably at 150 ° C using trichlorobenzene as eluent and a polystyrene as standard.
More preferably, the compounds of the present invention are polymers comprising at least 60% by weight of the units of formula 1 or 1’ based on the weight of the polymer.
Even more preferably, the compounds of the present invention are polymers comprising at least 80% by weight of the units of formula 1 or 1’ based on the weight of the polymer.
Most preferably, the compounds of the present invention are polymers comprising at least 95% by weight of the units of formula 1 or 1’ based on the weight of the polymer.
Preferably, X is at each occurrence 0, S or Se. More preferably, X is at each occurrence S or Se. Most preferably, X is at each occurence S.
Preferably, Y is at each occurrence 0, S or Se. More preferably, Y is at each occurrence S or Se. Most preferably, Y is at each occurence S.
Preferably Q is at each occurrence C or Si. More preferably Q is at each occurrence C. Preferably, R 1 is at each occurrence selected from the grou p consisting of H, C^ Q -alkyl, - wherein
o is an integer from 1 to 10,
p is an integer from 1 to 40,
R a is at each occu rrence C^o-alkyl, C 2-10 -alkenyl or C 2-10 -a I ky ny I,
q is an integer from 1 to 50,
R b is at each occurrence H or halogen, with the provisio that not all R b in - [CR b R b ] q - CR b R b R b are H,
Ci- -alkyl, C 2-50 -alkenyl and C 2-50 -a I kyny I can be substituted with one to fou r substitu ents independently selected from the group consisting of OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , N R C R C , N R c -C(0) R c , C(0)-N R c R c , N [C(0) R c ] [C(0) R c ], SR C , CN, and N0 2 , wherein
R c is at each occu rrence H, C^ Q -alkyl, C 2-10 -alkenyl or C 2-10 -a I ky ny I.
More preferably, R 1 is at each occurrence C 1-50 -alkyl. Most preferably, R 1 is at each occur rence C 6-30 -a I ky I.
Preferably, R 2 is at each occurrence H, Ci -30 -alkyl or halogen. More preferably, R 2 is at each occu rrence H.
Preferably, R 3 is at each occurrence H, C 1-30 -alkyl or halogen. More preferably, R 3 is at each occu rrence H.
Preferably, X, Q, R 1 and R 2 are at each occu rrence the same. If Y and R 3 are present, Y and R 3 are preferably at each occu rrence the same.
Preferably, n is 0, 1 or 2. More preferably, n is 0 or 1. Most preferably, n is 0.
Preferably, m is 0, 1, 2 or 3. More preferably, m is 0, 1 or 2. Most preferably, m is 1.
Preferably, U and L 2 are independently from each other and at each occu rrence selected from the grou p consisting of C 6-26 -arylene, 5 to 20 membered heteroarylene, and wherein C 6 -26 _ arylene and 5 to 20 membered heteroarylene can be substituted with one to fou r substituents R d at each occu rrence selected from the grou p consisting of Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to fou r substituents R d , is selected from the grou p consisting of
wherein
R 101 is at each occu rrence H or Ci -30 -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to fou r substi- tutents R d , are selected from the grou p consisting of
wherein
R 103 is at each occu rrence H, Ci -30 -alkyl, C 2-30 -alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occu rrence H or Ci -30 -a I ky I.
More preferably, U and L 2 are independently from each other and at each occurrence se lected from the grou p consisting of C 6-26 -arylene, 5 to 20 membered heteroarylene wherein
C 6.26 -arylene and 5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occu rrence selected from the grou p consisting of Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to two substituents R d , are select ed from the grou p consisting of
wherein
R 101 is at each occu rrence H or Ci -30 -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , are selected from the grou p consisting of
wherein
R 103 is at each occurrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen,
R 102 is at each occurrence H or Ci -30 -alkyl.
Even more preferably, L d and L 2 are independently from each other and at each occurrence selected from the group consisting of C 6-26 -arylene, 5 to 20 membered heteroarylene wherein
C 6.26 -arylene and 5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occurrence selected from the group consisting of Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to two substituents R d , is
wherein
R 101 is at each occu rrence H or Ci -30 -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , are selected from the grou p consisting of
wherein
R 103 is at each occu rrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occu rrence H or Ci -30 -alkyl.
Most preferably, U and L 2 are independently from each other a 5 to 20 membered het- eroarylene wherein
5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occurrence selected from the grou p consisting of Ci -30 -a I ky I, C 2-30 -alkenyl, C 2-30 - alkynyl and halogen, wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , is
Particular preferred com pou nds of the present invention are polymers com prising at least one u nit of formu la 1 or 1’, wherein n = 0, and which are of formu la
l’-IB
l’-IC wherein
X is at each occurrence 0, S or Se,
Q is at each occurrence C or Si,
R 1 is at each occu rrence C^ Q -alkyl,
R 2 is at each occu rrence H,
m is 0, 1 or 2,
L 2 is at each occurrence selected from the grou p consisting of C 6-26 -arylene, 5 to 20 mem bered heteroarylene wherein
C 6.26 -arylene and 5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occu rrence selected from the grou p consisting of C^ Q -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to two substituents R d , is
wherein
R 101 is at each occu rrence H or C^ Q -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , are selected from the grou p consisting of
wherein
R 103 is at each occu rrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occu rrence H or Ci -30 -alkyl.
More particular preferred com pou nds of the present invention are polymers com prising at least one u nit of formu la 1 or G, wherein n = 0 and which are of formu la W
10
wherein
X is at each occurrence O, S or Se,
Q is at each occurrence C or Si,
R 1 is at each occu rrence Ci -50 -alkyl,
R 2 is at each occu rrence H,
m is 0, 1 or 2,
L 2 is at each occurrence selected from the grou p consisting of C 6-26 -arylene, 5 to 20 mem bered heteroarylene wherein
C 6 -26 _ arylene and 5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occu rrence selected from the grou p consisting of Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to two substituents R d , is
wherein
R 101 is at each occu rrence H or Ci -30 -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , are selected from the grou p consisting of
wherein
R 103 is at each occu rrence H, C^ Q -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occu rrence H or C^ Q -alkyl.
Even more particu lar preferred compounds of the present invention are polymers compris ing at least one unit of formu la
wherein
X is at each occurrence O, S or Se,
Q is at each occurrence C or Si,
R 1 is at each occu rrence Ci -50 -alkyl,
R 2 is at each occu rrence H,
m is 0, 1 or 2,
L 2 is at each occurrence selected from the grou p consisting of C 6-26 -arylene, 5 to 20 mem bered heteroarylene wherein
C 6 -26 _ arylene and 5 to 20 membered heteroarylene can be substituted with one to two substituents R d at each occu rrence selected from the grou p consisting of Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I ky ny I and halogen, wherein C 6-26 -arylene, optionally substituted with one to two substituents R d , is
wherein
R 101 is at each occu rrence H or Ci -30 -alkyl, and wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , are selected from the group consisting of
wherein
R 103 is at each occurrence H, C^ Q -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen, R 102 is at each occurrence H or C^ Q -alkyl. Most particularly preferred compounds of the present invention are polymers comprising at least one unit of formula
wherein
X is at each occurrence 0, S or Se,
Q is at each occurrence C or Si,
R 1 is at each occurrence Ci -50 -alkyl,
R 2 is at each occurrence H,
m is 0, 1 or 2,
L 2 is at each occurence 5 to 20 membered heteroarylene wherein
5 to 20 membered heteroarylene can be substituted with one to two substituents R d which is at each occurrence halogen, wherein 5 to 20 membered heteroarylene, optionally substituted with one to two substi- tutents R d , is
Especially preferred compounds of the present invention are polymers comprising at least one unit of formula
wherein R 1 is at each occurrence Ci -50 -alkyl.
Also part of the present invention, is a process for the preparation of the compounds of the present invention comprising at least one unit of formula
wherein
Ml and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system;
X is at each occurrence 0, S, Se or Te, Q is at each occurrence C, Si or Ge,
R 1 is at each occurrence selected from the group consisting of H, Ci -50 -alkyl, -[CH 2 ] 0 -[0- SiR a R a ] p -OSiR a R a R a , -[CH 2 ] 0 -[R a R a Si-0] p -SiR a R a R a , -[CR b R b ] q -CR b R b R b , C 2-50 -alkenyl, C 2-50 - alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl and 5 to 14 membered heteroaryl, wherein
o is an integer from 0 to 10,
p is an integer from 1 to 40,
R a is at each occurrence Ci_i 0 -alkyl, C 2-10 -alkenyl or C 2-10 -alkynyl,
q is an integer from 1 to 50,
R b is at each occurrence H or halogen, with the provisio that not all R b in -[CR b R b ] q - CR b R b R b are H,
Ci-so-alkyl, C 2-50 -alkenyl and C 2-50 -a I kyny I can be substituted with one to four substitu ents independently selected from the group consisting of OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , NR C R C , NR c -C(0)R c , C(0)-NR c R c , N[C(0)R c ][C(0)R c ], SR C , CN, SiR c R c R c , and N0 2 ,
C 5-8 -cycloalkyl can be substituted with one or two substituents independently selected from the group consisting of Ci_i 0 -a I kyl, C 2-10 -alkenyl, C 2-10 -alkynyl, OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , NR C R C , NR c -C(0)R c , C(0)-NR c R c , N[C(0)R c ][C(0)R c ], SR C , halogen, CN, SiR c R c R c , and N0 2 ; and one CH 2 -group of C 5-8 -cycloalkyl can be replaced by O, S, OC(O), CO, NR C or NR c -CO,
Cg- -a ry I and 5 to 14 membered heteroaryl can be substituted with one to three sub stituents independently selected from the group consisting of Ci_i 0 -a I kyl, C 2-10 -alkenyl, nyl, OR c , OC(0)-R c , C(0)-OR c , C(0)-R c , NR C R C , NR c -C(0)R c , C(0)-NR c R c , ] [C(0)R c ], SR C , halogen, CN, and N0 2 , wherein
R c is at each occurrence H, Ci -20 -al kyl, C 2-10 -alkenyl or C 2-10 -alkynyl,
R 2 is at each occurrence H, Ci -30 -alkyl, C 2-30 -alkenyl or C 2-30 -a I kyny I or halogen, n is 0, 1, 2, 3 or 4,
m is 0, 1, 2, 3 or 4, and
L b and L 2 are independently from each other and at each occurrence selected from the group consisting of C 6-26 -arylene, 5 to 20 membered heteroarylene, wherein
C 6.26 -arylene and 5 to 20 membered heteroarylene can be substituted with one to four substituents R d at each occurrence selected from the group consisting of H, Ci -30 -alkyl, C 2-30 -alkenyl, C 2-30 -a I kyny I and halogen, and can be substituted with one or two substituents at each occurrence selected from the group consisting of R e , COOR e and CN, wherein R e is at each occurrence selected from the group consisting of H, Ci -30 -alkyl, C 2-3 o-alkenyl and C 2-30 -a I kyny I, which process comprises the step of treating a compound of formula
4
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for units of formul 1 or G with acid to afford a compound of formula
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for the units of formula 1 and 1’.
The acid can be any acid such as a cation exchanger in hydrogen form, trifluoroactic acid, acetic acid or p-toluene sulfonic acid. Preferably, the acid is a cation exchanger in hydrogen form, more preferably Amberlyst ® 15.
Preferably, the water formed in this step is removed in situ.
The step can be performed in any suitable solvent, for example toluene. The compounds of the present invention comprising at least one unit of formula 1 or 1’ can be prepared from compounds of formula 3 or 3 by methods known in the art.
The compounds of the present invention, which are polymers comprising at least a unit of formula 1 or 1’, wherein n = 0, and which are units of formula
or
wherein
Ml, M2, X, Q, R 1 , R 2 , m and L 2 are as defined for a formula 1 or 1’, can be prepared by treating a compound of formula
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for units of formula 1 or 1’, and Z 1 is at each occurence selected from the group consisting of B(OZ a )(OZ a ), SnZ a Z a Z a ,
wherein Z a is at each occurrence H or C 1-4 -alkyl, with a compound of formula wherein L 2 is as defined in units of formula 1 and 1’, and LG 2 is at each occurrence a leaving group.
For example, the compounds of the present invention, which are polymers comprising at least a unit of formula 1 or 1’, wherein n and m = 0 and which units are of formula
wherein
Ml, M2, X, Q, R 1 and R 2 are defined as in formula 1 or 1, can be prepared by treating a compound of formula
or
wherein Ml, M2, X, Q, R 1 and R 2 are defined as in formula 1 or 1’, and
Z 1 is at each occurence selected from the group consisting of B(OZ a )(OZ a ), SnZ a Z a Z a ,
wherein Z a is at each occurrence H or C 1-4 -alkyl,
with a compound of formula
or
wherei n M l, M2, X, Q, R 1 and R 2 are defined as in formula 1 or 1’, and
LG 3 is a leaving grou p.
Preferably, Z 1 is at each occurence selected from the group consisting of SnZ a Z a Z a and
wherein Z a is at each occurrence H or C 1-4 -alkyl.
More preferably, Z 1 is at each occu rence SnZ a Z a Z a , wherein Z a is at each occurrence Ci -4 - alkyl.
Preferably, LG 2 and LG 3 are independently and at each occu rrence halogen, more preferably Cl or Br.
The reaction is usually performed in the presence of a catalyst, preferably a Pd catalyst such as Pd(P(Ph) 3 ) 4 , Pd(OAc) 2 and tris(dibenzylideneacetone)dipalladiu m. Depending on the Pd catalyst, the reaction may also require the presence of a phosphine ligand such as P(Ph) 3 , P(o-tolyl) 3 and P(fe/7-Bu) 3 . The reaction is also usually performed at elevated tem peratures, such as at temperatu res in the range of 40 to 250 ° C, preferably 60 to 200 ° C. The reaction can be performed in the presence of any suitable solvent such as tetrahyd rofu- ran, toluene or chlorobenzene. The reaction is usually performed under inert gas.
When Z 1 is at each occurence SnZ a Z a Z a , wherein Z a is at each occu rrence Ci -4 -alkyl, the re action is usually performed in the presence of a catalyst, preferably a Pd catalyst such as Pd (P(Ph) 3 ) 4 and tris(dibenzylideneacetone)dipalladiu m .
The com pounds of formu la
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for units of formula 1 and 1’, and
Z 1 is at each occurence selected from the group consisting of B(OZ a )(OZ a ), SnZ a Z a Z a ,
wherein Z a is at each occurrence H or C 1-4 -alkyl,
can be prepared by treating a compound of formula
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for units of formula 1 or 1’, with a base and Z^LG 1 , wherein Z 1 is as defined in formula 2 or 2’, and LG 1 is a leaving group.
The base can be any suitable base such as n-butyl lithium.
Preferably, if Z 1 is SnZ a Z a Z a , LG 1 is is at each occurrence halogen, more preferably Br.
The compounds of formula 4, wherein Ml, Q, X, R 1 and R 2 are as defined for the units of formula 1, can be prepared as follows
8
The compounds of formula 8, wherein Ml, Q, X and R 1 are as defined for the units of formu la 1 and R 2 is H, can be prepared as follows
8-1 9-1
The compounds of formula 4’, wherein M2, Q, X, R 1 and R 2 are as defined for the units of formula 1’ and can be prepared as follows:
The compounds of formula 8’, wherein M2, Q, X and R 1 are as defined for the units of for mula 1’ and R 2 is H, can be prepared as follows
The compounds 10 and 10’ can be prepared by methods known in the art, for example as described in W. Zhang, J. Smith, S. E. Watkins, R. Gysel, M. McGehee, A. Salleo, J. Kirkpat rick, S. Ashraf, T. Anthopoulos, M. Heeney, I. McCulloch, J. Am. Chem. Soc. 2010, 132, 11437. Also part of the present invention are compounds of formula
or
wherein Ml, M2, X, Q, R 1 and R 2 are as defined for the units of formula 1 or 1’.
Preferred compounds of formula 3 or 3’ are of formula
3A
5
3D
15
wherein
X, Q, R 1 and R 2 are as defined above, and
Y is at each occurrence 0, S, Se or Te, and
R 3 is at each occurrence H, Ci -30 -alkyl, C 2-3 o-alkenyl or C 2-30 -a I ky ny I or halogen.
More preferred compounds of formula 3 or 3’ are compounds of formula 3A, 3B, 3C, 3D,
3Ά, 3’B and 3’C.
Even more preferred compounds of formula 3 or 3’ are compounds of formula 3A, 3B, 3C and 3D.
Most preferred compounds of formula 3 or 3’ are compounds of formula 3A.
Also part of the invention is an electronic device comprising the compounds of the present invention. The electronic device can be an organic photovoltaic device (OPVs), an organic field-effect transistor (OFETs), an organic light emitting diode (OLEDs) or an organic photodiode (OPDs).
Preferably, the electronic device is an organic photovoltaic device (OPVs), an organic field- effect transistor (OFETs) or an organic photodiode (OPDs).
More preferably, the electronic device is an organic field effect transistor (OFET).
Usually, an organic field effect transistor comprises a dielectric layer, a semiconducting lay er and a substrate. In addition, an organic field effect transistor usually comprises a gate electrode and source/drain electrodes.
Preferably, the semiconducting layer comprises the compounds of the present invention. The semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.
The dielectric layer comprises a dielectric material. The dielectric material can be silicon dioxide or aluminium oxide, or, an organic polymer such as polystyrene (PS),
poly(methylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), poly (vi nyl alcohol) (PVA), benzocyclobutene (BCB), fluoropolymers or polyimide (PI). The dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm.
The dielectric layer can in addition to the dielectric material comprise a self-assembled monolayer of organic silane derivates or organic phosphoric acid derivatives. An example of an organic silane derivative is octyltrich lorosilane. An examples of an organic phosphoric acid derivative is octyldecylphosphoric acid. The self-assembled monolayer comprised in the dielectric layer is usually in contact with the semiconducting layer.
The source/drain electrodes can be made from any suitable organic or inorganic
source/drain material. Examples of inorganic source/drain materials are gold (Au), silver (Ag) or copper (Cu), as well as alloys comprising at least one of these metals. The source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 20 to 70 nm.
The gate electrode can be made from any suitable gate material such as highly doped sili con, aluminium (Al), tungsten (W), indium tin oxide or gold (Au), or alloys comprising at least one of these metals. The gate electrode can have a thickness of 1 to 200 nm, prefera bly from 5 to 100 nm.
The substrate can be any suitable substrate such as glass, or a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and poly ethylene naphthalate (PEN). Depending on the design of the organic field effect transistor, the gate electrode, for example highly doped silicon can also function as substrate. The organic field effect transistor can be prepared by methods known in the art.
For example, a top-gate bottom-contact organic field effect transistor can be prepared as follows: Sorce/drain electrodes can be formed by evaporating a suitable source/drain mate rial, for example gold (Au), on photo- lithogra ph ical ly defined electrodes on a suitable sub strate, for example a glass substrate. The electrodes can be treated with a suitable elec trode treatment material such as pentafluorobenzenethiol. The semiconducting layer can be formed by depositing a solution of the compounds of the present invention, for example by spin-coating, on the source/drain electrodes. A dielectric layer can be formed by applying, for example, by spin-coating, a solution of a suitable dielectric material such as fluoropoly- mer, on the semiconducting layer. The gate electrode of a suitable gate material, for exam ple gold (Au), can be evaporated through a shadow mask on the dielectric layer.
Also part of the invention is the use of the compounds of the present invention as semicon ducting material.
The compounds of the present invention show high charge carrier mobilities. In addition, the compounds of the present invention show a high stability. Furthermore, the polymers of the present invention are compatible with liquid processing techniques.
Fig 1 shows the transfer characteristics of an organic field effect transistor comprising pol ymer PI as semiconducting material
Fig 2 shows the output characteristics of an organic field effect transistor comprising poly mer PI as semiconducting material.
Examples
Example 1
Preparation of compound 11a
Compound 13a: A solution of LDA in THF (1 M) (67.4 ml_, 67.4 mmol) was added dropwise to 3-bromothiophene (14a) (10 g, 61.3 mmol) in 300 ml_ THF at 0 ° C. After stirring the mix ture for 1 h, DM F (5.2 ml_, 67.4 mmol) was added to the mixture at 0 ° C and the mixture was warmed up to room temperature. After stirring for 4 h, water (100 ml_) was added to the mixture and it was extracted with ether for three times. The organic phases were col- lected, dried over magnesium sulfate, filtered and concentrated under vacuum. The product was purified by column chromatography on silica gel with hexane/ethyl acetate (50:1) as eluent to give compound 13a as a yellow oil. Yield: 11.0 g (94%). 3 H NMR (400 MHz; CDCI 3 ): 5 7.15 (d, 1H, J= 4.8 Hz), 7.73 (dd, 1H, J= 1.2, 5.2 Hz), 9.98 (d, 1H, J= 1.2 Hz); 13 C NMR (100 MHz; CDCI 3 ): 5 120.38, 132.03, 134.87, 136.90, 183.03.
Compound 12a: 3-bromothiophene-2-carbaldehyde(13a) (11 g, 57.6 mmol) was dissolved in methanol (300 ml) and cooled to 0 C. NaBH 4 (3.3 g, 86.4 mmol) was added in small por tions to the mixture and stirred for 4h. Water (100 ml_) was added to the mixture and it was extracted with ether for three times. The organic phases were collected, dried over magne sium sulfate, filtered and concentrated under vacuum. The product was purified by column chromatography on silica gel with hexane/ethyl acetate (10:1) as eluent to give compound 12a as a colourless oil. Yield: 10.9 g (98%). 3 H NMR (700 MHz, CDCI 3 ) 5 7.28 (d, 1H, J= 5.2 Hz), 6.98 (d, 1H, J= 5.2 Hz), 4.83 (d, 2H, J= 6.4 Hz), 2.98 (s, br, 1H); 13 C NMR (176 MHz, CDCI 3 ) 5 138.31, 130.13, 125.48, 108.89, 58.96.
Compound 11a: Imidazole (8.82 g, 129.5mmol) was added to a solution of (3- bromothiophen-2-yl)methanol (12a) (10 g, 51.8 mmol) and triisopropylch lorosi lane (11.98g, 62.16mmol) in dichloromethane. The mixture was stirred for 12 h, diluted with saturated aq. NH4CI, extracted with EtOAc, washed with brine and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent: Petroleum ether/ethyl acetate = 50:1) to provide compound 11a as a colorless solid (17.74 g, 98% yield). 3 HNMR (700 MHz, CDCI 3 ) 5 7.21 (d, J = 5.3 Hz, 1H), 6.92 (d, J = 5.3 Hz, 1H), 4.92 (s, 2H), 1.22 - 1.18 (m, 3H), 1.12 (s, 18H); 13 CNMR (176 MHz, CDCI 3 ) 5 140.83, 129.60, 124.39, 105.30, 61.23, 18.01, 12.01.
Example 2
Preparation of polymer PI comprising a unit of formula 1A
-61
9a
Compound 10a and compound 9a were synthesized as described in W. Zhang, J. Smith, S. E. Watkins, R. Gysel, M. McGehee, A. Salleo, J. Kirkpatrick, S. Ashraf, T. Anthopoulos, M.
Heeney, I. McCulloch, J. Am. Chem. Soc. 2010, 132, 11437.
Compound 8a: 4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaceno[l,2-b:5,6-b']d ithiophene (9a) (10 g, 8.59 mmol) was dissolved in anhydrous TH F (100 ml_) and cooled down to -78 ° C under argon, n-butyllithium solution (2.5M, 8.59 ml_) was added dropwise and the mixture was warmed up to 0 °C and stirred for 30min. The mixture was cooled down to -78 °C again and then 1 ml_ of DMF was added dropwise into the solution and the mixture was warmed up to room temperature and stirred for another 6 hours. Water (100 ml_) was added to the mixture and it was extracted with ethyl acetate for three times. The organic phases were collected, dried over magnesium sulfate, filtered and concentrated under vacuum. The product was purified by column chromatography on silica gel with hexane/ethyl acetate (5:1) as eluent to give compound 8a as a yellow solid (9.75 g, 93% yield). 3 H NMR (500 MHz, CDCI 3 ) 5 9.94 (s, 1H), 7.66 (s, 1H), 7.48 (s, 1H), 2.12-2.10 (m, 8H), 1.36-0.92 (m, 104H), 0.91-0.87 (m, 12H), 0.82-0.65 (m, 8H); 13 C N MR (126 MHz, CDCI 3 ) 5 182.96, 156.06, 155.18, 151.40, 145.60, 136.47, 130.41, 115.03, 53.81, 39.12, 32.11, 30.12, 29.84, 29.76, 29.43, 24.32, 22.81, 14.22.
Compound 7a: (3-bromothiophen-2-yl)methoxy)triisopropylsilane (11a) (5 g, 14.3 mmol), prepared as described in example 1, was dissolved in 100 ml_ anhydrous diethyl ether and cooled to -78 °C, n-Butyllithium solution (2.5M, 5.72 ml_) was added dropwise stirred for 30m in. 4, 4, 9, 9-tetrahexadecy 1-4, 9-dihydro-s-indaceno[l,2-b:5,6-b'] dithiophene-2, 7- dicarbaldehyde (8a) (5.82 g, 4.76 mmol) dissolved in 50 ml_ anhydrous diethyl ether was added dropwise into the solution and stirred for further 30min. The mixture was warmed up to room temperature and stirred overnight. Water (150 ml_) was added to the mixture and it was extracted with ethyl acetate for three times. The organic phases were collected, dried over magnesium sulfate, filtered and concentrated under vacuum. The product was purified by column chromatography on silica gel with hexane/dichloromethane (3:1) as eluent to give compound 7a as a brown liquid (6.04 g, 72% yield). 3 H NMR (700 MHz, CDCI 3 ) d 7.26 (s, 2H), 7.16 (s, 2H), 7.14 (d, J = 5.2 Hz, 2H), 7.03 (d, J = 5.2 Hz, 2H), 6.17 (d, J = 4.8 Hz, 2H), 4.97 (s, 4H), 2.15-2.10 (m, 8H), 1.23-1.14 (m, 6H), 1.34-0.97 (m, 140H), 0.91-0.82 (m, 12H), 0.81-0.65 (m, 8H); 13 C N MR (176 MHz, CDCI 3 ) d 171.19, 154.24, 152.54, 148.90, 145.69, 141.11, 140.71, 139.54, 135.67, 128.11, 126.40, 124.23, 123.09, 122.98, 119.11, 112.79, 60.43, 31.96, 29.76, 29.71, 29.41, 22.73, 21.08, 18.03, 18.01, 17.99, 17.73, 14.22, 14.16, 12.02, 11.95.
Compound 6a: Com pou nd 7a (10.87 g, 6.17 mmol) was dissolved in 100 m l_ dich loro- methane and then Zn l 2 (0.40 g, 1.24 mmol) was added in one portion, followed by the addi tion of NaBH 3 CN (1.17 g, 18.52 m mol). The mixture was stirred overnight and then quenched by Water (100 m l_). The mixture was extracted with ethyl acetate for th ree times. The or ganic phases were collected, dried over magnesium su lfate, filtered and concentrated u nder vacuu m. The product was purified by colum n ch romatography on silica gel with hexane as eluent to give com pou nd 6a as a yellow liquid (10.04 g, 94% yield).
H N M R (700 M Hz, CDCI 3 ) 5 7.26 (s, 2H), 7.14 (d, J = 5.1 Hz, 2H), 6.87 (d, J = 5.1 Hz, 2H), 6.65 (s, 2H), 4.96 (s, 4H), 4.14 (s, 4H), 2.15-2.10 (m, 8H), 1.28-1.14 (m, 6H), 1.34-0.96 (m, 140H), 0.91-0.85 (m, 12H), 0.82-0.64 (m, 8H); 13 C N M R (176 M Hz, CDCI 3 ) 5 154.43, 152.29, 145.05, 139.98, 139.90, 135.51, 134.85, 129.04, 126.84, 123.09, 121.23, 119.68, 112.50, 59.59, 41.36, 39.07, 36.09, 31.96, 29.75, 27.70, 24.24, 22.73, 20.48, 18.62, 17.85, 14.17, 12.97, 11.48.
Compound 5a: Com pou nd 6a (5.58 g, 3.23 m mol) was dissolved in 100 ml_ TH F and TBAF (1M in TH F, 8.07 m l_) was added into the solution and the mixture was stirred overnight and then quenched by Water (100 ml_). The mixture was extracted with ethyl acetate for th ree times. The organic phases were collected, d ried over magnesium su lfate, filtered and con centrated under vacuu m. The product was pu rified by colu m n chromatography on silica gel with hexane/dich loromethane (1:1) as eluent to give compou nd 5a as a yellow liquid (4.35 g, 95% yield). 3 H N M R (700 M Hz, CDCI 3 ) 5 7.26 (s, 2H), 7.21 (d, J = 5.1 Hz, 2H), 6.93 (d, J = 5.1 Hz, 2H), 6.69 (s, 2H), 4.83 (s, 4H), 4.21 (s, 4H), 2.14-2.12 (m, 8H), 1.32-0.97 (m, 104H), 0.91-0.84 (m, 12H), 0.82-0.64 (m, 8H); 13 C N M R (176 M Hz, CDCI 3 ) 5 171.26, 154.54, 152.31,
145.13, 140.06, 137.83, 137.71, 135.49, 129.52, 124.29, 119.71, 112.55, 60.46, 57.78, 53.94, 39.07, 31.96, 30.08, 29.75, 29.71, 29.69, 29.46, 29.41, 24.23, 22.73, 21.09, 17.73, 14.22, 14.17, 12.29.
Compound 4a: Com pou nd 5a (5.22 g, 3.68 m mol) was dissolved in 100 ml_ dichloromethane and Dess-Martin periodinane (3.91 g, 9.22 mmol) was added into the solution and the mix tu re was stirred overnight and then slowly quenched by satu rated NaHC0 3 solution. The mixtu re was stirred at room tem peratu re for 30min and then satu rated NaS 2 S0 3 solution was added. The mixtu re was extracted with ethyl acetate for th ree times. The organic phas es were collected, d ried over magnesiu m sulfate, filtered and concentrated u nder vacuu m. The product was pu rified by colu mn chromatography on silica gel with hex
ane/dich loromethane (1:1) as eluent to give com pou nd 4a as a yellow solid (4.52 g, 87% yield). 3 H N M R (700 M Hz, CDCI 3 ) 5 10.13 (s, 2H), 7.65 (d, J = 5.0 Hz, 2H), 7.14 (s, 2H), 7.05 (d, J = 5.0 Hz, 2H), 6.74 (s, 2H), 4.56 (s, 4H), 2.13-2.11 (m, 8H), 1.36-0.96 (m, 104H), 0.90- 0.86 (m, 12H), 0.83-0.69 (m, 8H); 13 C N M R (176 M Hz, CDCI 3 ) 5 182.09, 154.69, 152.44,
149.14, 143.00, 141.50, 140.61, 137.85, 135.50, 134.50, 131.27, 131.08, 128.42, 128.26, 53.93, 39.01, 31.90, 30.25, 29.71, 29.73, 29.63, 29.41, 29.49, 24.22, 22.71, 21.39, 17.43, 14.12, 14.10, 12.49. Compound 3a: 3,3'-((4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaceno[l,2-b:5 ,6- b']dithiophene-2,7-diyl)bis(methylene))bis(thiophene-2-carba ldehyde) (4a) (3.77 g, 2.67 m mol) was dissolved in 100 ml_ toluene and 5g Amberlyst-15 was added into the solution and the mixtu re was refluxed overnight and the water generated in situ was removed by a Dean-Stark Trap. The mixture was filtered, and the filtrate was concentrated under vacuu m. The crude product was pu rified by colu mn chromatography on silica gel with hexane as elu ent to give com pou nd 3a as a pale yellow solid (2.28 g, 62% yield). J H N M R (700 M Hz, CD 2 CI 2 ) 5 8.37 (s, 2H), 8.31 (s, 2H), 7.52 (s, 2H), 7.51 (d, J = 5.3 Hz, 2H), 7.41 (d, J = 5.4 Hz, 2H), 2.13-2.11 (m, 8H), 1.34-0.96 (m, 104H), 0.91-0.86 (m, 12H), 0.82-0.69 (m, 8H); 13 C N M R (176 M Hz, CD 2 CI 2 ). 13C N M R (176 M Hz, CDCI3) 5 139.07, 131.37, 127.83, 126.75, 122.52, 122.09, 121.64, 117.43, 111.44, 108.12, 103.46, 99.16, 98.40, 40.43, 24.10, 16.91, 14.67, 14.65, 14.64, 14.61, 14.58, 14.46, 14.35, 14.17, 8.78, 7.68, 0.90.
Compound 2a: Com pou nd 3a (3.42 g, 2.49 m mol) was dissolved in 80 m l_ TH F and cooled to -78 °C, n-butyllithiu m solution (2.5M, 2.49 m l_) was added dropwise stirred for 30min.
6.23 ml_ Me 3 SnCI solution (1M in TH F) was added dropwise into the solution and the mix tu re was warmed u p to room temperatu re and stirred overnight and then quenched by water (80 ml_). The mixtu re was extracted with ethyl acetate for th ree times. The organic phases were collected, concentrated under vacuu m. The product was recrystallized in acetoni- trile/dich loromethane to afford com pou nd 2a as a pale yellow solid. (4.02 g, 95% yield). J H N M R (500 M Hz, CD 2 CI 2 ) 5 8.36 (s, 1 H), 8.32 (s, 2H), 7.53 (s, 2H), 7.50 (s, 2H), 2.53 - 2.34 (m, 4H), 2.34 - 2.16 (m, 4H), 1.41 - 0.95 (m, 104 H), 0.93-0.86 (m, 12H), 0.84-0.61 (m, 8H) 0.50 (s, 18H).
Polymer PI: A 2.5 ml_ microwave vial was charged with com pou nd 2a (0.40 g, 0.233 mmol), 4,7-dibromobenzo[c] [l,2,5]thiadiazole(0.068 g, 0.233 m mol) , 2 mol% of
tris(dibenzylideneacetone)dipalladium (2.9 mg, 0.005 m mol) and tri (o-tolyl) phosphine (6 mg, 0.02 mmol). The vial was sealed and chlorobenzene (1 m l_) was added. The obtained solution was degassed with argon for 30 minutes. The vial was subjected to the following reaction conditions in the microwave reactor: 2 minutes at 100° C, 2 minutes at 120° C, 5 minutes at 140° C, 5 minutes at 160° C and 20 minutes at 180° C. The polymer was end- capped by addition of 0.1 eq. of 2-bromobenzene before the reaction mixtu re was resubmit ted to the microwave reactor, 1 minute at 100° C, 1 minute at 120° C, 2 minutes at 140° C and 5 minutes at 160° C. The polymeric solution was cooled down and 0.1 eq. of 2- (trimethylstan nyl)benzene was added by syringe. The reaction vial was subjected to the previously mentioned temperature scheme to finalize the end-capping reaction. After reac tion, the crude polymer was precipitated in methanol and then fu rther pu rified by Soxh let extractions with acetone, hexane and chloroform for 24 hou rs each. Remaining palladium residues were removed by treating a polymeric chloroform solution with an aqueous sodiu m diethyldithiocarbamate solution for 2 hours at 50° C u nder vigorous stirring. Afterwards the organic phase was separated from the aqueous phase and washed several times with wa ter. The polymeric solution was concentrated u nder reduced pressure and precipitated into cold methanol. Polymer PI was filtered off and d ried u nder high vacuu m for at least 24 hours. J H NMR (500 MHz, CDCI 3 ) 5 8.71 (br, 2H), 8.37 (br, 2H), 8.13 (br, 2H), 7.68 (br, 2H), 7.74 (br, 2H), 2.14-2.10 (br, 8H), 0.95-1.32 (br, 104H), 0.91-0.84 (br, 12H), 0.82-0.61 (br, 8H).
Example 3
Preparation of a bottom-contact, top-gate organic fieldeffect transistor (OFET) comprising polymer PI as semiconducting material
Gold source and drain contacts were evaporated on glass, followed by treatment with pen- tafluorobenzenethiol. The semiconducting layer was then spin-coated from 10 mg mL 1 so lution of polymer PI in chlorobenzene and Cytop ® , a commercially available fluoropolymer, was deposited as gate dielectric. An Ag gate electrode was used. The channel width and length are W = 1000 mΐti and L = 30 mΐti.
The transfer and output characteristics of the OFET were measured.
Figure 1 and 2 show the transfer and output characteristics of the OFET.
Field effect mobility was calculated using the standard thin film transistor model in the saturation regime of the device using:
where L, W, and C are the channel length, channel width, and capacitance of the dielectric, respectively.
The average saturation hole mobility of the OFET was 2.5 cm 2 V 1 s \ with an on/off ratio of 2 x 10 5 and approximately -17 V threshold voltage.