1.-14. (canceled)
15. A polymer, comprising a repeating unit of the formula
wherein
R1 is hydrogen, C1-C100alkyl, or a group of formula \u2014SiR501R502R503;
R2 is \u2014CN, \u2014CF3, a fluorine atom, or a group of the formula
R301, R302 and R303 are independently of each other C1-C18alkyl, C1-C18alkyl which is substituted by E\u2032 andor interrupted by D\u2032, C1-C100fluoroalkyl, C3-C12cycloalkyl, C6-C24aryl, C6-C24aryl group, which is be substituted by G\u2032; C2-C18alkenyl, C2-C18alkynyl, C7-C25aralkyl, or C7-C25aralkyl which is substituted by G\u2032; C2-C20heteroaryl, or C2-C20heteroaryl, which is substituted by G\u2032;
R601 and R602 are independently of each other H, or C1-C25alkyl;
R501, R502 and R503 are independently of each other C1-C8alkyl, C6-C24aryl, or C7-C12aralkyl;
D\u2032 is \u2014CO\u2014, \u2014COO\u2014, \u2014S\u2014, \u2014SO\u2014, \u2014SO2\u2014, \u2014O\u2014, \u2014NR65\u2014, \u2014SiR70R71\u2014, \u2014POR72\u2014, \u2014CR63\u2550CR64\u2014, or \u2014C\u2261C\u2014, and
E\u2032 is \u2014OR69, \u2014SR69, \u2014NR65R66, \u2014COR68, \u2014COOR67, \u2014CONR65R66, \u2014CN, CF3, or halogen,
G\u2032 is E\u2032, C1-C18alkyl, or C1-C18alkyl which is interrupted by \u2014O\u2014,
R63 and R64 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by \u2014O\u2014;
R65 and R66 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by \u2014O\u2014; or
R65 and R66 together form a five or six membered ring,
R67 is C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl;
or C1-C18alkyl which is interrupted by \u2014O\u2014,
R68 is H; C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by \u2014O\u2014,
R69 is C6-C18aryl; C6-C18aryl, which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by \u2014O\u2014,
R70 and R71 are independently of each other C1-C18alkyl, C6-C18aryl, or C6-C18aryl, which is substituted by C1-C18alkyl, and
R72 is C1-C18alkyl, C6-C18aryl, or C6-C18aryl, which is substituted by C1-C18alkyl.
16. The polymer according to claim 15, which is a polymer comprising a repeating unit of the formula
wherein
R1 is hydrogen, or C1-C100alkyl,
R301 is C1-C18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C1-C18alkyl, halogen, OR69, CN, or CF3; wherein R69 is C1-C18alkyl, or phenyl;
R601 and R602 are the same and are hydrogen or C1-C18alkyl.
17. The polymer according to claim 15, which is a polymer comprising a repeating unit of the formula
wherein
R1 is hydrogen, or C1-C100alkyl, and
R601 and R602 are the same and are hydrogen, or C1-C18alkyl.
18. The polymer according to claim 15, wherein the polymer is a polymer of formula
or a polymer, comprising repeating units of the formula
wherein
n is in the range of 4 to 1000,
A is a repeating unit of formula (I), and
\u2014COM1- is a repeating unit
wherein
k is 0, 1, 2, or 3; 1 is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3;
Ar4, Ar5, Ar6 and Ar7 are independently of each other a group of formula and
wherein
X1 is \u2014O\u2014, \u2014S\u2014, \u2014NR8\u2014, \u2014Si(R11)(R11\u2032)\u2014, \u2014Ge(R11)(R11\u2032)\u2014, \u2014C(R7)(R7\u2032)\u2014, \u2014C(\u2550O)\u2014,
wherein
X1\u2032 is S, O, NR107\u2014, \u2014Si(R117)(R117\u2032)\u2014, \u2014Ge(R117)(R117\u2032)\u2014, \u2014C(R108)(R109)\u2014, \u2014C(\u2550O)\u2014, \u2014C(\u2550CR104R104\u2032)\u2014,
R3 and R3\u2032 are independently of each other hydrogen, halogen, halogenated C1-C25alkyl, cyano, C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms;
C7-C25arylalkyl, or C1-C25alkoxy;
R104 and R104\u2032 are independently of each other hydrogen, cyano, COOR103, a C1-C25alkyl group, or C6-C24aryl or C2-C20heteroaryl,
R4, R4\u2032, R5, R5\u2032, R6, and R6\u2032 are independently of each other hydrogen, halogen, halogenated C1-C25alkyl, cyano, C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C7-C25arylalkyl, or C1-C25alkoxy;
R7, R7\u2032, R9 and R9\u2032 are independently of each other hydrogen, C1-C25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms; or C7-C25arylalkyl,
R8 and R8\u2032 are independently of each other hydrogen, C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; or C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C7-C25arylalkyl,
R11 and R11\u2032 are independently of each other C1-C25alkyl group, C7-C25arylalkyl, or a phenyl group, which are optionally substituted one to three times with C1-C8alkyl andor C1-C8alkoxy;
R12 and R12\u2032 are independently of each other hydrogen, halogen, cyano, C1-C25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C1-C25alkoxy, C7-C25arylalkyl, or
wherein R13 is a C1-C10alkyl group, or a tri(C1-C8alkyl)silyl group; or
R104 and R104\u2032 are independently of each other hydrogen, C1-C18alkyl, C6-C10aryl, which are optionally substituted by G, or C2-C8 heteroaryl, which is optionally substituted by G,
R105, R105\u2032, R106 and R106\u2032 are independently of each other hydrogen, halogen, cyano, C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms;
C7-C25arylalkyl, or C1-C18alkoxy,
R107 is hydrogen, C7-C25arylalkyl, C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18perfluoroalkyl; C1-C25alkyl; which is optionally interrupted by \u2014O\u2014, or \u2014S\u2014; or \u2014COOR103;
R108 and R109 are independently of each other H, C1-C25alkyl, C1-C25alkyl which is substituted by E andor interrupted by D, C7-C25arylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-C18alkenyl, C2-C18alkynyl, C1-C18alkoxy, C1-C18alkoxy which is substituted by E andor interrupted by D, or C7-C25aralkyl, or
R108 and R109 together form a group of formula \u2550CR110R111, wherein
R110 and R111 are independently of each other H, C1-C18alkyl, C1-C18alkyl which is substituted by E andor interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2-C20heteroaryl, or C2-C20heteroaryl which is substituted by G, or
R108 and R109 together form a five or six membered ring, which optionally can be substituted by C1-C18alkyl, C1-C18alkyl which is substituted by E andor interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-C18alkenyl, C2-C18alkynyl, C1-C18alkoxy, C1-C18alkoxy which is substituted by E andor interrupted by D, or C7-C25aralkyl,
D is \u2014CO\u2014, \u2014COO\u2014, \u2014S\u2014, \u2014O\u2014, or \u2014NR112\u2032\u2014,
E is C1-C8thioalkoxy, C1-C8alkoxy, CN, \u2014NR112\u2032R113\u2032, \u2014CONR112\u2032R113\u2032, or halogen,
G is E, or C1-C18alkyl, and
R112\u2032 and R113\u2032 are independently of each other H; C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by \u2014O\u2014,
R115 and R115\u2032 are independently of each other hydrogen, halogen, cyano, C1-C25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C1-C25alkoxy, C7-C25arylalkyl, or
wherein R116 is a C1-C18alkyl group, or a tri(C1-C8alkyl)silyl group;
R117 and R117\u2032 are independently of each other C1-C25alkyl group, C7-C25arylalkyl, or a phenyl group, which are optionally substituted one to three times with C1-C8alkyl andor C1-C8alkoxy;
R118, R119, R120 and R121 are independently of each other hydrogen, halogen, halogenated C1-C25alkyl, cyano, C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C7-C25arylalkyl, or C1-C25alkoxy;
R122 and R122\u2032 are independently of each other hydrogen, C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy; or C1-C25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C7-C25arylalkyl.
R201 is selected from hydrogen, a C1-C100alkyl group, \u2014COOR103, a C1-C100alkyl group substituted by one or more halogen atoms, hydroxyl groups, nitro groups, \u2014CN, or C6-C18aryl groups andor interrupted by \u2014O\u2014, \u2014COO\u2014, \u2014OCO\u2014 or \u2014S\u2014; a C7-C25arylalkyl group, a carbamoyl group, a C5-C12cycloalkyl group, which are substituted one to three times with C1-C100alkyl andor C1-C100alkoxy, a C6-C24aryl group, which are optionally substituted one to three times with C1-C100alkyl, C1-C100thioalkoxy, andor C1-C100alkoxy; and pentafluorophenyl;
R103 and R114 are independently of each other C1-C25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms,
R202 and R203 may be the same or different and are selected from H, F, \u2014CN, C1-C100alkyl, which are optionally interrupted by one or more oxygen, or sulphur atoms; and C1-C100alkoxy.
19. The polymer according to claim 15, comprising repeating units of the formula
wherein
A is a repeating unit of formula (I), and
COM1- is a repeating unit of formula
wherein
R3, R3\u2032, R4 and R4\u2032 are independently of each other hydrogen, or C1-C25alkyl;
R8 and R8\u2032 are independently of each other hydrogen, or C1-C25alkyl;
R114 is a C1-C38alkyl group;
R201 is a C1-C38alkyl group; and
R202 and R203 are independently of each other hydrogen or C1-C25alkyl.
20. The polymer according to claim 18, which is a polymer of formula
wherein n is 4 to 1000,
A is a repeating unit of formula
wherein R1 is selected from hydrogen, or C1-C25alkyl,
R301 is C1-C18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C1-C18alkyl, halogen, OR69, CN, or CF3; wherein R69 is C1-C18alkyl, or phenyl;
R601 and R602 are hydrogen; and
is a group of formula
wherein R3, R3\u2032, R4 and R4\u2032 are independently of each other hydrogen, or C1-C25alkyl; and
R201 is a C1-C38alkyl group.
21. The polymer according to claim 19, which is a polymer of the formula
wherein
n is 4 to 1000;
R1 is hydrogen or C1-C100alkyl,
R3 and R3\u2032 are independently of each other hydrogen or C1-C25alkyl;
R201 is a C1-C38alkyl group,
R301 is C1-C18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C1-C18alkyl, halogen, OR69, CN, or CF3; wherein R69 is C1-C18alkyl, or phenyl;
R601 and R602 are independently of each other hydrogen, or C1-C25alkyl.
22. An organic semiconductor material, layer or component, comprising the polymer according to claim 15.
23. An electronic device, comprising the polymer according to claim 15.
24. The electronic device according to claim 23, wherein the electronic device is an organic light emitting diode, an organic photovoltaic device, a photodiode, or an organic field effect transistor.
25. A process for the preparation of an electronic device, which process comprises applying a solution andor dispersion of the polymer according to claim 15 in an organic solvent to a suitable substrate and removing the solvent.
26. A method comprising incorporating the polymer according to claim 15 into organic light emitting diodes, photovoltaic devices, photodiodes, or organic field effect transistors.
27. A compound of the formula
X2-A-X2\u2032\u2003\u2003(V),
wherein
X2 and X2\u2032 are independently of each other halogen, ZnX12, \u2014SnR207R208R209, wherein R207, R208 and R209 are identical or different and are H or C1-C6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X12 is a halogen atom; SiR210R211R212, wherein R210, R211 and R212 are identical or different and are halogen, or C1-C6alkyl; \u2014OS(O)2CF3, \u2014OS(O)2-aryl, \u2014OS(O)2CH3, \u2014B(OH)2, \u2014B(OY1)2,
\u2014BF4Na, or \u2014BF4K, wherein Y1 is independently in each occurrence a C1-C10alkyl group and Y2 is independently in each occurrence a C2-C10alkylene group and Y13 and Y14 are independently of each other hydrogen, or a C1-C10alkyl group.
28. A process for the preparation of a polymer of formula
comprising reacting a dihalogenide of formula X10-A-X10 with an equimolar amount of a diboronic acid or diboronate corresponding to formula
or reacting a dihalogenide of formula
with an equimolar amount of a diboronic acid or diboronate corresponding to formula X11-A-X11, wherein X10 is halogen, and X11 is independently in each occurrence \u2014B(OH)2, \u2014B(OY1)2,
wherein Y1 is independently in each occurrence a C1-C10alkyl group and Y2 is independently in each occurrence a C2-C10alkylene group and Y13 and Y14 are independently of each other hydrogen, or a C1-C10alkyl group, in a solvent and in the presence of a catalyst; or
reacting a dihalogenide of formula X10-A-X10 with an equimolar amount of an organo tin compound corresponding to formula
or reacting a dihalogenide of formula
with an equimolar amount of an organo tin compound corresponding to formula X11\u2032-A-X11\u2032, wherein
X11\u2032 is independently in each occurrence \u2014SnR207R208R209, wherein R207, R208 and R209 are identical or different and are H or C1-C6alkyl, or two of the groups R207, R208 and R209 form a ring and these groups are optionally branched, A and COM1 are as defined in claim 18, X10 is as defined above and n is in the range of 4 to 1000.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A method for treating the surface of oxide glass, which comprises contacting the surface of oxide glass with a gas of a fluorinating agent or a mixed gas having a fluorinating agent diluted with an inert gas, wherein the fluorinating agent is an elemental fluorine, or a fluorine compound capable of cleaving a bond between an oxygen atom and a metal atom in the framework of the oxide glass and forming a bond between a fluorine atom and the metal atom; and the concentration of hydrogen fluoride at the surface of oxide glass with which the fluorinating agent is in contact, is controlled to be at most 1 mol %.
2. The method for treating the surface of oxide glass according to claim 1, wherein the concentration of hydrogen fluoride at the surface of oxide glass with which the fluorinating agent is in contact, is controlled to be at most 1 mol % by carrying out the procedure of contacting the surface of oxide glass with a gas of a fluorinating agent or a mixed gas having a fluorinating agent diluted with an inert gas, in a closed container containing the gas of a fluorinating agent or the mixed gas having a fluorinating agent diluted with an inert gas, and a solid metal fluoride.
3. The method for treating the surface of oxide glass according to claim 1, wherein the concentration of hydrogen fluoride at the surface of oxide glass with which the fluorinating agent is in contact, is controlled to be at most 1 mol % by carrying out a procedure of contacting the surface of oxide glass with the fluorinating agent in a gas phase by setting the oxide glass in a pipe line in which the gas of a fluorinating agent or the mixed gas having a fluorinating agent diluted with an inert gas, continuously flows.