1. A compound of the formula (1)
M(L)n(L\u2032)m\u2003\u2003formula (1)
where the compound contains a moiety M(L)n is selected from the formulae (36) to (59)
wherein
X is CR1;
R1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R2)2, CN, NO2, Si(R2)3, B(OR2)2, C(\u2550O)R2, P(\u2550O)(R2)2, S(\u2550O)R2, S(\u2550O)2R2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylakoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C\u2550CR2, C\u2261C, Si(R2)2, Ge(R2)2, Sn(R2)2, C\u2550O, C\u2550S, C\u2550Se, C\u2550NR2, P(\u2550O)(R2), SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a diarylamino group, diheteroarylamino group or aryiheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of two or more of these groups; two or more radicals R1 here may also form a mono- or polycyclic, aliphatic, aromatic andor benzo-fused ring system with one another;
M is iridium or platinum;
L\u2032 is, identically or differently on each occurrence, a co-ligand;
W is, identically or differently on each occurrence, a radical of the formulae (3) and (4)
where V is equal to S or O;
R4 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R2)2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C\u2550CR2, C\u2261C, Si(R2)2, Ge(R2)2, Sn(R2)2, C\u2550O, C\u2550S, C\u2550Se, C\u2550NR2, P(\u2550O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of two or more of these groups; two or more radicals R4 here may also form a mono- or polycyclic, aliphatic, aromatic andor benzo-fused ring system with one another;
R2 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R3)2, CN, NO2, Si(R3)3, B(OR3)2, C(\u2550O)R3, P(\u2550O)(R3)2, S(\u2550O)R3, S(\u2550O)2R3, OSO2R3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH2 groups is optionally replaced by R3C\u2550CR3, C\u2261C, Si(R3)2, Ge(R3)2, Sn(R3)2, C\u2550O, C\u2550S, C\u2550Se, C\u2550NR3, P(\u2550O)(R3), SO, SO2, NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R3, or an aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R3, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R3, or a combination of two or more of these groups; two or more adjacent radicals R2 here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
R3 is, identically or differently on each occurrence, H, D, F or an aliphatic, aromatic andor heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R3 here optionally also forms a mono- or polycyclic, aliphatic or aromatic ring system with one another;
n is 1, 2 or 3 for M equal to iridium and is 1 or 2 for M equal to platinum;
m is 0, 1, 2 for M equal to iridium and is 0 or 1 for M equal to platinum;
the indices n and m here are selected so that the coordination number on the metal corresponds to 6 for M equal to iridium or rhodium and corresponds to 4 for M equal to platinum or palladium.
2. The compound according to claim 1, wherein the moiety M(L)n is selected from the formulae (36), (40), (44), (48), (52), and (56).
3. The compound according to claim 1, wherein the radical W is given by the formulae (110) to (115)
where
R5 is, identically or differently on each occurrence, H, D, a straight-chain alkyl or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C\u2550CR2, C\u2261C, Si(R2)2, Ge(R2)2, Sn(R2)2, C\u2550O, C\u2550S, C\u2550Se, C\u2550NR2, P(\u2550O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of two or more of these groups; two or more radicals R1 here optionally also forms a mono- or polycyclic, aliphatic, aromatic andor benzo-fused ring system with one another.
4. The compound according to claim 1, wherein M is equal to iridium.
5. The compound according to claim 1, wherein m=0.
6. A process for the preparation of the compound according to claim 1 which comprises reacting the corresponding free ligands with metal alkoxides of the formula (344), with metal ketoketonates of the formula (345) or with metal halides of the formula (346)
where the symbols M, n and R1 have the meanings indicated in claim 1 and Hal=F, Cl, Br or I.
7. A formulation comprising at least one compound according to claim 1 and at least one solvent.
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 composition comprising a polymerization product of an anionic polysaccharide, a diisocyanate, and a linker,
wherein the linker comprises i) an ether group, an ester group, or a combination thereof and, ii) a chain extender comprising a hydroxyl group, a thiol group, an amine group, or a combination thereof.
2. The composition of claim 1, wherein the polymerization product comprises a copolymer a prepolymer and the linker, wherein:
the prepolymer comprises a copolymer of the anionic polysaccharide and the diisocyanate.
3. The composition of claim 2, wherein the prepolymer comprises at least one segment represented by IBABBABnI, wherein, independently for each occurrence, A represents a polysaccharide block, B represents a urethane or urea block, I represents an isocyanate and n represents and integer ranging from 1 to 10,000.
4. The composition of claim 1, wherein the linker comprises at least one segment represented by ECE, wherein, independently for each occurrence, C represents an ether block, an ester block or a combination thereof, and E represents a chain extender comprising a hydroxyl, a thiol or an amine group.
5. The composition of claim 1, wherein the polymerization product comprises at least one segment represented by BABBABnBCBBABBABn, wherein, independently for each occurrence, A represents a polysaccharide block, B represents a urea or urethane block, C represents an ether block, and ester block or a combination thereof, and n represents an integer ranging from 1 to 10,000.
6. The composition of claim 5, wherein the polymerization product further comprises at least one isocyanate group.
7. The composition of claim 1, wherein the polymerization product comprises a copolymer of a prepolymer and the anionic polysaccharide, wherein:
the prepolymer comprises a copolymer of the linker and the diisocyanate.
8. The composition of claim 7, wherein the prepolymer comprises at least one segment represented by IBCBI, wherein I represents and isocyanate, B represents a urea or a urethane, and C represents an ether block, an ester block, or a combination thereof.
9. The copolymer of claim 1, wherein the polymerization product comprises at least one segment represented by ABBCBBA, wherein independently for each occurrence, A represents a polysaccharide block, B represents a urea or urethane block, and C represents an ether block, an ester block, or a combination thereof.
10. The composition of claim 1, wherein the polymerization product comprises cross-links.
11. The composition of claim 1, wherein the anionic polysaccharide is selected from the group consisting of hyaluronic acid, a glycosaminoglycan, aligante, cellulose, carboxymethylcellulose, carboxymethylamylose, chondroitin-6-sulfate, dermatin sulfate, salts thereof, and mixtures thereof.
12. The composition of claim 1, wherein the anionic polysaccharide is hyaluronic acid or a salt thereof.
13. The composition of claim 1 wherein at least one hydrolysis product of the diisocyanate is a biocompatible diamine.
14. The copolymer of claim 1, wherein the diisocyanate is an aliphatic diisocyanate, a cyclocloaliphatic diisocyanate or an aromatic dissociate.
15. The copolymer of claim 1, wherein the linker comprises ether groups.
16. The copolymer of claim 15, wherein the ether groups comprise ethylene oxide and propylene oxide monomeric units.
17. The copolymer of claim 16, wherein the number ratio of ethylene oxide to propylene oxide ranges from about 65:35 to about 85:15 ethylene oxide:propylene oxide.
18. The copolymer of claim 16, wherein the number ratio of ethylene oxide to propylene oxide ranges from about 35:65 to about 15:85 ethylene oxide:propylene oxide.
19. The copolymer of claim 17, wherein the weight ratio of polysaccharide to ether ranges from about 85:15 to about 65:35 polysaccharide:ether.
20. The copolymer of claim 18, wherein the weight ratio of the polysaccharide to ether ranges from about 35:65 to about 15:85 polysaccharide:ether.
21. The copolymer of claim 1, wherein the linker comprises a hydroxyacid.
22. A medical device comprising a composition comprising a polymerization product of an anionic polysaccharide, a diisocyanate, and a linker,
wherein the linker comprises i) an ether group, an ester group, or a combination thereof and, ii) a chain extender comprising a hydroxyl group, a thiol group, an amine group, or a combination thereof.
23. The medical device of claim 22, wherein the device is a mesh comprising the composition.
24. The medical device of claim 22, wherein the device is a mesh coated with the composition.
25. The medical device of claim 23, wherein the mesh comprises fibers comprising the composition.
26. The medical device of claim 23, wherein the mesh is coupled to an anti-adhesive film.
27. The medical device of claim 22, wherein the device is an implantable medical device coated with the composition.
28. The medical device of claim 22, wherein the device is a film comprising the composition.
29. The medical device of claim 22, wherein the device is a composite film comprising an anti-adhesion film coupled to a film comprising the composition.
30. A method for reducing protein adsorption to a medical device in vivo, comprising providing a medical device comprising a composition comprising a polymerization product of an anionic polysaccharide, a diisocyanate, and a linker,
wherein the linker comprises i) an ether group, an ester group, or a combination thereof and, ii) a chain extender comprising a hydroxyl group, a thiol group, an amine group, or a combination thereof.