TETRA-NUCLEAR NEUTRAL COPPER (I) COMPLEXES WITH DIARYLPHOSPHINE LIGANDS

Abstract

The present invention relates to tetra-nuclear neutral copper (I) complexes that have a cubane-like structure, wherein said complexes further comprise diarylphosphine ligands which are bonded via phosphorus atoms. Furthermore, the present invention refers to methods for generating such copper (I) complex and to uses thereof. The present invention further relates to cubane-like conjugates that comprise moiety of the copper (I) complexes of the invention. Formula (A), each L is independently from each other an optionally substituted diary lphosphine residue of Formula (A1): PHSr.sub.2 (A1).

##STR00001##

Claims

1. A copper (I) complex of Formula (A) ##STR00040## wherein: each Cu is copper (I); each X is independently from each other halogen; each L is independently from each other an optionally substituted diarylphosphine residue of Formula (A1):
PHAr2   (A1), wherein: P is phosphorus; H is hydrogen; and each Ar is independently from each other an aryl residue that is unsubstituted or substituted by one or more substituents, wherein a substituent may optionally be or contribute to a linker that interconnects two ligands L with another; wherein the phosphorus is bound to Cu; and wherein said copper (I) complex has a neutral net charge.

2. The copper (I) complex of claim 1, wherein each X is iodine.

3. The copper (I) complex of claim 1, wherein each Ar is independently from each other a phenyl residue Ph that is unsubstituted or substituted by one or more substituents each independently from each other selected from the group consisting of a linear or branched, unsubstituted or substituted C.sub.1-C.sub.20-alkyl residue, a linear or branched, unsubstituted or substituted C.sub.1-C.sub.12-alkoxy residue and halogen, wherein each substituent may optionally be or contribute to a linker that interconnects two ligands L with another.

4. The copper (I) complex of any of claim 1, wherein each ligand L independently from each other has a structure of Formula (A2) ##STR00041## wherein R1 to R10 are independently from each other selected from the group consisting of hydrogen, a linear or branched, unsubstituted or substituted C.sub.1-C.sub.20-alkyl residue, or a linear or branched, unsubstituted or substituted C.sub.1-C.sub.12-alkoxy residue, and wherein the phosphorus is bound to Cu.

5. The copper (I) complex of claim 1, wherein each ligand L independently from each other has a structure of Formula (A2) ##STR00042## wherein each of R1 to R10 is independently from each other selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, or a C4-alkyl, and wherein the phosphorus is bound to Cu.

6. The copper (I) complex of claim 1, wherein each L is a monovalent ligand of the same kind.

7. The copper (I) complex of claim 1, wherein two L are interconnected with another, thereby forming a bivalent ligand.

8. The copper (I) complex of any of claim 1, wherein said copper (I) complex has the following structure or Formula (A3): ##STR00043## wherein each Ph is independently from each other an unsubstituted or substituted phenyl residue.

9. A method for generating a copper (I) complex of claim 1, said method comprising the following steps: providing, in an inert atmosphere: (a) copper (I) halide, (b) an electronically neutral substituted ligand L as defined in claim 1, and (c) a solvent in which components (a) and (b) are dissolved; (ii) incubating the composition of step (i) at conditions allowing the formation of the copper (I) complex; and (iii) optionally removing the solvent and obtaining a solid residue; and (iv) optionally mixing the composition of step (ii) or a solution obtained by dissolving the solid residue of step (iii) with an anti-solvent, thereby forming a precipitate, and subsequently drying the precipitate.

10. A method for generating a cubane-like conjugate CC, said method comprising the following steps: (I) providing, in an inert atmosphere: (A) a copper (I) complex of claim 1, (B) an unsaturated moiety to be conjugated thereto; and (C) a solvent in which components (A) and (B) are dissolved; (II) incubating the composition of step (I) at conditions allowing the reaction of the unsaturated moiety (B) with the phosphorus atom of the ligand L; (III) optionally adding polymer monomers to the solution of step (II) and initiating polymerization; and (IV) optionally removing the solvent.

11. A cubane-like conjugate CC obtainable from a method of claim 10.

12. A cubane-like conjugate CC comprising at least one copper (I) complex moiety of Formula (A-iii) ##STR00044## wherein: each Cu is copper (I); each X is independently from each other halogen; each P is phosphorus; each R is independently from each other hydrogen or —R.sup.a—R.sup.b, wherein in at least one ligand L residue R is —R.sup.a—R.sup.b; each Ar is independently from each other an aryl residue as defined in claim 1; R.sup.a is an unsubstituted or substituted C.sub.1-C.sub.20-alkylene residue; and R.sup.b is a polymeric residue, a C.sub.2-C.sub.20-(hetero)aromatic residue, or a C.sub.1-C.sub.20-alkoxy residue, wherein each hydrogen may optionally be substituted by an halogen or deuterium, wherein said copper (I) complex has a neutral net charge.

13. An opto-electronic device containing a copper (I) complex of claim 1.

14. (canceled)

15. (canceled)

16. An opto-electronic device containing the cubane-like conjugate CC of claim 11.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0214] FIG. 1 shows the three-dimensional structure of a copper (I) complex of the present invention. In the depicted example, the copper (I) complex is based on a cubane-like structure of CuI bound to four hydrogenodiphenylphosphine ligands.

[0215] FIG. 2 shows the three-dimensional structure of a copper (I) complex of the present invention, wherein the atoms except the hydrogen atoms are highlighted.

[0216] In the depicted example, the copper (I) complex is based on a cubane-like structure of CuI bound to four hydrogenodiphenylphosphine ligands.

EXAMPLES

[0217] Synthesis of a copper (I) complex of the present invention (CuI-diphenylphosphine complex having cubane-like structure):

[0218] Copper(I) Iodide, diphenylphosphine (also: hydrogenodiphenylphosphine) and dry toluene (or dry (methyl)tetrahydrofurane) were placed in a flame-dried Schlenck tube under argon. The solution was heated at 110° C. during 24 hours. Then the mixture was cooled down to room temperature (RT) and the solvent was removed under vacuum. The solid residue was dissolved in dichloromethane (CH.sub.2O1.sub.2) and the solution was poured into diethyl ether (Et.sub.2O). The copper (I) complex precipitates directly and was filtrated and washed several times with Et.sub.2O. The product was dried under vacuum.

[0219] It was further found that other solvents can be used instead of toluene such as, e.g., dichloromethane or tetrahydrofuran (THF) depending of the solubility of phosphines.

[0220] The following copper (I) complex was obtained:

##STR00014##

[0221] .sup.1H NMR (500 MHz, CDCl.sub.3): 5.82 (d, J=315.6 Hz, 4 H), 7.18 (m, 16 H), 7.26 (m, 8 H), 7.49 (m, 16 H) ppm.

[0222] .sup.13C NMR (126 MHz, CDCl.sub.3): δ128.57(d, J=9 Hz), 129.59, 130.32(d, J=29 Hz), 134.1(d, J=12.4 Hz) ppm.

[0223] .sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-39 (br) ppm.

[0224] Anal. Calcd for C.sub.64H.sub.68Cu.sub.4I.sub.4O.sub.4P.sub.4: C, 38.26; H, 2.94. Found: C, 36.49; H, 2.82.

[0225] IR (neat) v=2975, 1476, 1437, 1089, 887, 819, 725, 686 cm.sup.−1

[0226] ATG: 5% per mass lost at 257° C.

[0227] Determining the Structure:

[0228] The three-dimensional (3D) (crystal) structure was determined by means of NMR. The results are depicted in FIGS. 1 and 2. The following distances and angles have been determined. The numbers correspond to those depicted in FIG. 2.

TABLE-US-00001 TABLE 1 Distances determined for the Cul cubane- like core structure: No. Objects Length 1 Cu1 Cu2 2.8735(8) 2 Cu1 I2 2.6799(7) 3 Cu1 I1 2.6826(8) 4 Cu1 I1 2.6759(6) 5 Cu1 P1 2.251(1) 6 Cu1 Cu2 2.8132(9) 7 Cu1 Cu1 2.8158(7) 8 Cu1 Cu2 2.8735(8) 9 Cu1 I2 2.6799(7) 10 Cu1 I1 2.6826(8) 11 Cu1 I1 2.6759(6) 12 Cu1 P1 2.251(1) 13 Cu1 Cu2 2.8132(9) 14 Cu2 I2 2.6807(6) 15 Cu2 I2 2.6901(8) 16 Cu2 I1 2.6793(7) 17 Cu2 P2 2.248(1) 18 Cu2 I2 2.6807(6) 19 Cu2 P2 2.248(1) 20 Cu2 I2 2.6901(8) 21 Cu2 I1 2.6793(7) 22 Cu2 Cu2 3.0539(9)

TABLE-US-00002 TABLE 2 Angles determined for the Cul cubane- like core structure: No. compared objects Angle 1 Cu1 Cu1 Cu2 61.39(2) 2 Cu1 Cu1 I1 58.18(2) 3 Cu1 Cu2 I1 57.49(2) 4 Cu1 Cu2 I2 57.57(2) 5 Cu1 Cu2 Cu1 59.35(2) 6 Cu1 Cu2 I2 103.39(2) 7 Cu1 Cu2 I2 58.23(2) 8 Cu1 I1 Cu2 64.90(2) 9 Cu1 I1 Cu1 63.40(2) 10 Cu1 I2 Cu2 64.83(2) 11 Cu1 I2 Cu2 63.19(2) 12 Cu1 Cu1 Cu2 61.39(2) 13 Cu1 Cu1 I1 58.18(2) 14 Cu1 Cu1 P1 149.68(4) 15 Cu1 Cu1 Cu2 59.26(2) 16 Cu1 Cu1 I1 58.41(2) 17 Cu1 Cu1 I2 105.23(2) 18 Cu1 Cu2 I2 58.23(2) 19 Cu1 Cu2 P2 144.69(4) 20 Cu1 Cu2 Cu1 59.35(2) 21 Cu1 Cu2 I1 58.41(2) 22 Cu1 Cu2 I2 105.27(2) 23 Cu1 Cu2 I1 57.49(2) 24 Cu1 Cu2 I2 57.57(2) 25 Cu1 I1 Cu1 63.40(2) 26 Cu1 I1 Cu2 63.29(2) 27 Cu1 I1 Cu2 64.90(2) 28 Cu1 I2 Cu2 64.83(2) 29 Cu2 Cu1 I1 57.61(2) 30 Cu2 Cu1 I2 57.60(2) 31 Cu2 Cu1 Cu1 59.26(2) 32 Cu2 Cu1 Cu2 64.95(2) 33 Cu2 Cu1 I1 109.12(2) 34 Cu2 Cu1 I1 58.30(2) 35 Cu2 I1 Cu1 63.29(2) 36 Cu2 I2 Cu2 69.30(2) 37 Cu2 Cu1 I1 58.30(2) 38 Cu2 Cu1 P1 138.04(4) 39 Cu2 Cu1 Cu2 64.95(2) 40 Cu2 Cu1 I1 111.13(2) 41 Cu2 Cu1 I2 58.59(2) 42 Cu2 Cu1 I1 57.61(2) 43 Cu2 Cu1 I2 57.60(2) 44 Cu2 I2 Cu1 63.19(2) 45 Cu2 I2 Cu2 69.30(2) 46 I1 Cu1 I2 110.19(2) 47 I1 Cu1 Cu1 58.41(2) 48 I1 Cu1 Cu2 111.13(2) 49 I1 Cu1 I1 109.18(2) 50 I1 Cu2 I2 110.06(2) 51 I1 Cu2 Cu1 58.41(2) 52 I1 Cu2 I2 113.46(2) 53 I1 Cu1 P1 107.82(4) 54 I1 Cu1 Cu2 109.12(2) 55 I1 Cu1 I1 109.18(2) 56 I1 Cu1 I2 113.69(2) 57 I1 Cu1 I2 110.19(2) 58 I1 Cu2 I2 110.06(2) 59 I2 Cu1 Cu1 105.23(2) 60 I2 Cu1 Cu2 58.59(2) 61 I2 Cu1 I1 113.69(2) 62 I2 Cu2 Cu1 105.27(2) 63 I2 Cu2 I2 103.83(2) 64 I2 Cu2 P2 111.87(4) 65 I2 Cu2 Cu1 103.39(2) 66 I2 Cu2 I1 113.46(2) 67 I2 Cu2 I2 103.83(2) 68 P1 Cu1 Cu2 143.02(4) 69 P1 Cu1 I1 110.81(4) 70 P1 Cu1 I2 105.08(4) 71 P1 Cu1 Cu1 149.68(4) 72 P1 Cu1 Cu2 138.04(4) 73 P1 Cu1 I1 107.82(4) 74 P1 Cu1 Cu2 143.02(4) 75 P1 Cu1 I1 110.81(4) 76 P1 Cu1 I2 105.08(4) 77 P2 Cu2 Cu1 144.68(4) 78 P2 Cu2 I1 107.56(4) 79 P2 Cu2 I2 110.04(4) 80 P2 Cu2 Cu1 144.69(4) 81 P2 Cu2 I2 111.87(4) 82 P2 Cu2 Cu1 144.68(4) 83 P2 Cu2 I1 107.56(4) 84 P2 Cu2 I2 110.04(4)

TABLE-US-00003 TABLE 3 Angles determined for the copper (I) complex structure: No. Atoms Angle 1 C1 C2 H2 120.5 2 C1 C2 C3 119.2(5) 3 C1 C6 C5 120.2(6) 4 C1 C6 H6 119.9 5 C1 P1 C7 103.5(2) 6 C1 P1 Cu1 116.9(2) 7 C1 P1 H1P 98(2) 8 C1 C2 H2 120.5 9 C1 C2 C3 119.2(5) 10 C1 C6 C5 120.2(6) 11 C1 C6 H6 119.9 12 C1 P1 C7 103.5(2) 13 C1 P1 Cu1 116.9(2) 14 C1 P1 H1P 98(2) 15 C10 C11 H11 120.2 16 C10 C11 C12 119.7(7) 17 C10 C11 H11 120.2 18 C10 C11 C12 119.7(7) 19 C11 C12 H12 119.2 20 C11 C12 H12 119.2 21 C12 C7 P1 119.7(4) 22 C12 C7 P1 119.7(4) 23 C13 C14 H14 119.3 24 C13 C14 C15 121.2(6) 25 C13 C18 C17 121.7(6) 26 C13 C18 H18 119.2 27 C13 P2 C19 103.5(3) 28 C13 P2 Cu2 118.4(2) 29 C13 P2 H2P 103(2) 30 C13 C14 H14 119.3 31 C13 C14 C15 121.2(6) 32 C13 C18 C17 121.7(6) 33 C13 C18 H18 119.2 34 C13 P2 C19 103.5(3) 35 C13 P2 Cu2 118.4(2) 36 C13 P2 H2P 103(2) 37 C14 C13 C18 117.5(5) 38 C14 C13 P2 120.0(4) 39 C14 C15 H15 120.0 40 C14 C15 C16 120.0(7) 41 C14 C13 C18 117.5(5) 42 C14 C13 P2 120.0(4) 43 C14 C15 H15 120.0 44 C14 C15 C16 120.0(7) 45 C15 C16 H16 120.1 46 C15 C16 C17 119.9(7) 47 C15 C16 H16 120.1 48 C15 C16 C17 119.9(7) 49 C16 C17 H17 120.2 50 C16 C17 C18 119.6(7) 51 C16 C17 H17 120.2 52 C16 C17 C18 119.6(7) 53 C17 C18 H18 119.1 54 C17 C18 H18 119.1 55 C18 C13 P2 122.5(4) 56 C18 C13 P2 122.5(4) 57 C19 C20 H20 119.8 58 C19 C20 C21 120.4(7) 59 C19 C24 C23 119.2(7) 60 C19 C24 H24 120.4 61 C19 P2 Cu2 117.2(2) 62 C19 P2 H2P 98(2) 63 C19 C20 H20 119.8 64 C19 C20 C21 120.4(7) 65 C19 C24 C23 119.2(7) 66 C19 C24 H24 120.4 67 C19 P2 Cu2 117.2(2) 68 C19 P2 H2P 98(2) 69 C2 C1 C6 120.5(5) 70 C2 C1 P1 119.6(4) 71 C2 C3 H3 119.7 72 C2 C3 C4 120.8(6) 73 C2 C1 C6 120.5(5) 74 C2 C1 P1 119.6(4) 75 C2 C3 H3 119.7 76 C2 C3 C4 120.8(6) 77 C20 C19 C24 117.9(7) 78 C20 C19 P2 123.3(6) 79 C20 C21 H21 119.8 80 C20 C21 C22 120.3(7) 81 C20 C19 C24 117.9(7) 82 C20 C19 P2 123.3(6) 83 C20 C21 H21 119.8 84 C20 C21 C22 120.3(7) 85 C21 C22 H22 119.5 86 C21 C22 C23 120.9(7) 87 C21 C22 H22 119.5 88 C21 C22 C23 120.9(7) 89 C22 C23 H23 119.2 90 C22 C23 C24 121.3(7) 91 C22 C23 H23 119.2 92 C22 C23 C24 121.3(7) 93 C23 C24 H24 120.4 94 C23 C24 H24 120.4 95 C24 C19 P2 118.8(6) 96 C24 C19 P2 118.8(6) 97 C3 C4 H4 120.2 98 C3 C4 C5 119.6(6) 99 C3 C4 H4 120.2 100 C3 C4 C5 119.6(6) 101 C4 C5 H5 120.1 102 C4 C5 C6 119.7(6) 103 C4 C5 H5 120.1 104 C4 C5 C6 119.7(6) 105 C5 C6 H6 119.9 106 C5 C6 H6 119.9 107 C6 C1 P1 119.9(4) 108 C6 C1 P1 119.9(4) 109 C7 C8 H8 119.9 110 C7 C8 C9 120.1(5) 111 C7 C12 C11 121.4(6) 112 C7 C12 H12 119.4 113 C7 P1 Cu1 117.7(2) 114 C7 P1 H1P 98(2) 115 C7 C8 H8 119.9 116 C7 C8 C9 120.1(5) 117 C7 C12 C11 121.4(6) 118 C7 C12 H12 119.4 119 C7 P1 Cu1 117.7(2) 120 C7 P1 H1P 98(2) 121 C8 C7 C12 118.1(5) 122 C8 C7 P1 122.2(4) 123 C8 C9 H9 119.7 124 C8 C9 C10 120.6(6) 125 C8 C7 C12 118.1(5) 126 C8 C7 P1 122.2(4) 127 C8 C9 H9 119.7 128 C8 C9 C10 120.6(6) 129 C9 C10 H10 119.9 130 C9 C10 C11 120.2(7) 131 C9 C10 H10 119.9 132 C9 C10 C11 120.2(7) 133 Cu1 P1 H1P 119(2) 134 Cu1 Cu1 Cu2 61.39(2) 135 Cu1 Cu1 I1 58.18(2) 136 Cu1 Cu2 I1 57.49(2) 137 Cu1 Cu2 I2 57.57(2) 138 Cu1 Cu2 Cu1 59.35(2) 139 Cu1 Cu2 I2 103.39(2) 140 Cu1 Cu2 I2 58.23(2) 141 Cu1 I1 Cu2 64.90(2) 142 Cu1 I1 Cu1 63.40(2) 143 Cu1 I2 Cu2 64.83(2) 144 Cu1 I2 Cu2 63.19(2) 145 Cu1 P1 H1P 119(2) 146 Cu1 Cu1 Cu2 61.39(2) 147 Cu1 Cu1 I1 58.18(2) 148 Cu1 Cu1 P1 149.68(4) 149 Cu1 Cu1 Cu2 59.26(2) 150 Cu1 Cu1 I1 58.41(2) 151 Cu1 Cu1 I2 105.23(2) 152 Cu1 Cu2 I2 58.23(2) 153 Cu1 Cu2 P2 144.69(4) 154 Cu1 Cu2 Cu1 59.35(2) 155 Cu1 Cu2 I1 58.41(2) 156 Cu1 Cu2 I2 105.27(2) 157 Cu1 Cu2 I1 57.49(2) 158 Cu1 Cu2 I2 57.57(2) 159 Cu1 I1 Cu1 63.40(2) 160 Cu1 I1 Cu2 63.29(2) 161 Cu1 I1 Cu2 64.90(2) 162 Cu1 I2 Cu2 64.83(2) 163 Cu2 P2 H2P 114(2) 164 Cu2 Cu1 I1 57.61(2) 165 Cu2 Cu1 I2 57.60(2) 166 Cu2 Cu1 Cu1 59.26(2) 167 Cu2 Cu1 Cu2 64.95(2) 168 Cu2 Cu1 I1 109.12(2) 169 Cu2 Cu1 I1 58.30(2) 170 Cu2 I1 Cu1 63.29(2) 171 Cu2 I2 Cu2 69.30(2) 172 Cu2 P2 H2P 114(2) 173 Cu2 Cu1 I1 58.30(2) 174 Cu2 Cu1 P1 138.04(4) 175 Cu2 Cu1 Cu2 64.95(2) 176 Cu2 Cu1 I1 111.13(2) 177 Cu2 Cu1 I2 58.59(2) 178 Cu2 Cu1 I1 57.61(2) 179 Cu2 Cu1 I2 57.60(2) 180 Cu2 I2 Cu1 63.19(2) 181 Cu2 I2 Cu2 69.30(2) 182 H10 C10 C11 119.9 183 H10 C10 C11 119.9 184 H11 C11 C12 120.1 185 H11 C11 C12 120.1 186 H14 C14 C15 119.5 187 H14 C14 C15 119.5 188 H15 C15 C16 120.0 189 H15 C15 C16 120.0 190 H16 C16 C17 119.9 191 H16 C16 C17 119.9 192 H17 C17 C18 120.2 193 H17 C17 C18 120.2 194 H2 C2 C3 120.3 195 H2 C2 C3 120.3 196 H20 C20 C21 119.8 197 H20 C20 C21 119.8 198 H21 C21 C22 119.9 199 H21 C21 C22 119.9 200 H22 C22 C23 119.6 201 H22 C22 C23 119.6 202 H23 C23 C24 119.5 203 H23 C23 C24 119.5 204 H3 C3 C24 119.5 205 H3 C3 C24 119.5 206 H4 C4 C5 120.3 207 H4 C4 C5 120.3 208 H5 C5 C6 120.1 209 H5 C5 C6 120.1 210 H8 C8 C9 120.0 211 H8 C8 C9 120.0 212 H9 C9 C10 119.8 213 H9 C9 C10 119.8 214 I1 Cu1 I2 110.19(2) 215 I1 Cu1 Cu1 58.41(2) 216 I1 Cu1 Cu2 111.13(2) 217 I1 Cu1 I1 109.18(2) 218 I1 Cu2 I2 110.06(2) 219 I1 Cu2 Cu1 58.41(2) 220 I1 Cu2 I2 113.46(2) 221 I1 Cu1 P1 107.82(4) 222 I1 Cu1 Cu2 109.12(2) 223 I1 Cu1 I1 109.18(2) 224 I1 Cu1 I2 113.69(2) 225 I1 Cu1 I2 110.19(2) 226 I1 Cu2 I2 110.06(2) 227 I2 Cu1 Cu1 105.23(2) 228 I2 Cu1 Cu2 58.59(2) 229 I2 Cu1 I1 113.69(2) 230 I2 Cu2 Cu1 105.27(2) 231 I2 Cu2 I2 103.83(2) 232 I2 Cu2 P2 111.87(4) 233 I2 Cu2 Cu1 103.39(2) 234 I2 Cu2 I1 113.46(2) 235 I2 Cu2 I2 103.83(2) 236 P1 Cu1 Cu2 143.02(4) 237 P1 Cu1 I1 110.81(4) 238 P1 Cu1 I2 105.08(4) 239 P1 Cu1 Cu1 149.68(4) 240 P1 Cu1 Cu2 138.04(4) 241 P1 Cu1 I1 107.82(4) 242 P1 Cu1 Cu2 143.02(4) 243 P1 Cu1 I1 110.81(4) 244 P1 Cu1 I2 105.08(4) 245 P2 Cu2 Cu1 144.68(4) 246 P2 Cu2 I1 107.56(4) 247 P2 Cu2 I2 110.04(4) 248 P2 Cu2 Cu1 144.69(4) 249 P2 Cu2 I2 111.87(4) 250 P2 Cu2 Cu1 144.68(4) 251 P2 Cu2 I1 107.56(4) 252 P2 Cu2 I2 110.04(4)

[0229] Polymer Synthesis:

[0230] The above obtained copper (I) complex (CuI-diphenylphosphine complex having cubane-like structure) is dissolved in dry acetonitrile (or CH.sub.2Cl.sub.2) and placed in a flame-dried Schlenck tube under argon. divinylbenzene (4 equivalents) is added and the solution was heated at 70° C. during 7 hours. Then, styrene is introduced and the polymerization is initiated. After two hours, the solvent is removed under vacuum. The polystyrene solid residue is dried and may be investigated or treated further.

[0231] Synthesis of Conjugates:

[0232] Conjugates of conjugates with one type of ligands were prepared according to the following scheme:

##STR00015##

[0233] Herein, the reaction was conducted under UV light (e.g., at 455 nm) obtained by a light-emitting diode (LED) (e.g., LED 455). Dichloromethane (DCM) was used as solvent. The reaction was conducted at room temperature (rt) for 1-4 hours. The unsaturated moiety (B) (R—CH═CH.sub.2) was used in slight excess of 4.2 equivalents (eq). For different unsaturated residues, dependent on the residue R, the following percentage yields (Rdt %) were obtained:

TABLE-US-00004 TABLE 4 Percentage yields (Rdt %) of conjugates, wherein the dashed line indicates the binding site to a —CH═CH.sub.2 moiety (acrylate derivative) and the waved line indicates the binding site to a —C(CH.sub.3)═CH.sub.2 moiety (methacrylate derivative). R Rdt % —Ph 96 —PhBr 93 [00016] 97 [00017] 76 [00018] 69 [00019] 86 [00020] 84 [00021] 73 [00022] 79 [00023] 61 [00024] 58 [00025] 63 [00026] 59 [00027] 47

[0234] Alternative Process for Synthesis of Conjugates:

[0235] CuI-diphenylphosphine complex was dissolved in dry acetonitrile (or dichloromethane) and placed in a flame-dried Schlenck tube under argon. The acrylate derivative (here: styrene, para-phenylbromide or divinylbenzene) was added and the solution was heated at 70° C. during 7 hours. Then the mixture was cooled down to room temperature (RT) and the solvent was removed under vacuum. The solid residue was dissolved in dichloromethane and the solution was poured into diethyl ether. The complex precipitated directly and was filtrated and washed several times with diethyl ether and hexane. The product was dried under vacuum.

[0236] Alternative Process for Synthesis of Conjugates:

[0237] CuI-diphenylphosphine complex was dissolved in dry dichloromethane and placed in a flame-dried Schlenck tube under argon. The acrylate derivative was added and the solution was incubated for 6 hours. Then the mixture was cooled down to room temperature (RT) and the solvent was removed under vacuum. The solid residue was dissolve in dichloromethane and the solution was poured into diethyl ether or hexane. The complex precipitated directly and was filtrated and washed several times with diethyl ether and hexane. The product was dried under vacuum.

[0238] For example, the following conjugates were obtained:

##STR00028##

[0239] .sup.1H NMR (500 MHz, CDCl.sub.3): δ2.63 (m, 8 H), 2.91 (m, 8 H), 7.20 (m, 20 H), 7.28 (m, 24 H), 7.57 (m, 16 H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ30.04 (d, J=16.1 Hz), 30,96 (d, J=6.2 Hz),125,128.35 (d), 128.45 (d, J=8 Hz),129.51, 133.15(d, J=12 Hz), 133.41(d, J=26 Hz), 142.63 (d, J=14.7 Hz) ppm. .sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-29.49 (br) ppm. IR (neat) v=3048, 3026, 1599, 1482, 1434, 1096, 1026, 938, 730, 688 cm.sup.−1

##STR00029##

[0240] .sup.1H NMR (500 MHz, CDCl.sub.3): δ2.57 (m, 8 H), 2.81 (m, 8 H), 6.98 (m, 8 H), 7.28 (m, 32 H), 7.60 (m, 16 H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ29.5 (d, J=16.1 Hz), 30,96 (d, J=6.2 Hz), 119, 128.53 (d, J=8 Hz),129.71, 130.04, 131.37, 133.15(d, J=13 Hz), 133.16(d), 141.4 (d, J=15 Hz) ppm. .sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-29.28 (br) ppm IR (neat) v=3043, 1482, 1431, 1099, 1070, 1009, 936, 844, 800, 732, 693 cm.sup.−1

##STR00030##

[0241] .sup.1H NMR (500 MHz, CDCl.sub.3): δ7.60-7.50 (m, 16 H), 7.39-7.32 (m, 8 H), 7.31-7.25 (m, 16 H), 2.69-2.56 (m, 8 H), 2.51-2.51 (m, 8 H), 1.91 (s, 12 H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ173.17; 133.65 (d); 133.24 (d); 129.76; 128.68 (d); 38.75 (d); 29.80 (d, J=8 Hz); 22.19 ppm..sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-29.53 (br) ppm. Anal. Calcd for C.sub.64 H.sub.68Cu.sub.4I.sub.4O.sub.4P.sub.4: C, 43.02; H, 3.84. Found: C, 43.61; H, 3.92. IR (neat) v=3053, 2912, 1710, 1575, 1487, 1434, 1356, 1215, 1159, 1099, 868, 739, 693 cm−.sup.1. ATG: 5% per mass lost at 317° C.

[0242] This compound has an emission maximum of 606 nm, an excitation maximum of 340 nm and a quantum yield of 17%.

##STR00031##

[0243] .sup.1H NMR (500 MHz, CDCl.sub.3): δ7.70 (m, 8 H), 7.65 (m, 8 H), 7.31 (m, 24 H), 4.44 (m, 4 H), 2.96 (m, 8 H), 2.80 (m, 8 H), 2.31 (m, 4 H), 1.72 (m, 8 H), 1.51 (m, 8 H), 1.27 (m, 16 H), 1.15 (d,.sup.1J=7.0 Hz, 12 H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ18.76(d, J=7 Hz), 23.56 (d, J=Hz), 25.39, 30.44 (d , J=15.5 Hz), 31.31 (d, J=6 Hz)), 36.35(d, J=7.0 Hz), 72.57, 128.30 (t), 129.27 (d), 133.02 (d, J=12.6 Hz)), 134.24(d, J=13.5 Hz)), 175.45(d, J=9 Hz)) ppm. .sup.31P {.sup.1 H} NMR (203 MHz, CDCl.sub.3): δ-30 (br) ppm. IR (neat) v=3069, 2928, 2855, 1722, 1450, 1430, 1194, 1153, 1012, 912, 740, 695 cm.sup.−1

[0244] This compound has an emission maximum of 569 nm, an excitation maximum of 300 nm and a quantum yield of 61%.

##STR00032##

[0245] .sup.1H NMR (500 MHz, CDCl.sub.3): δ0.85 (t, 12 H), 1.29 (m, 8 H), 1.55 (m, 8 H), 2.55 (m, 16 H), 3.96 (t, 8 H), 7.31 (m, 24 H), 7.60 (m, 16 H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ13.74, 19.15, 20.02 (d, J=17.3 Hz), 26.94, 30.66 (d, J=8 Hz), 64.58, 128.52 (d, J=9 Hz), 129.73, 132.81 (d, J=29 Hz), 134.78 (d, J=12.0 Hz)), 173.34 (d, J=17 Hz) ppm. .sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-29(br) ppm. IR (neat) v=3057, 2993, 2871, 1729, 1459, 1431, 1156, 1016, 734, 696 cm.sup.−1

[0246] This compound has an emission maximum of 569 nm, an excitation maximum of 310 nm and a quantum yield of 60%.

##STR00033##

[0247] .sup.1 H NMR (500 MHz, CDCl.sub.3): δH=1.15 (t, 12 H), 2.52 (m, 16 H), 4.01 (m, 8 H), 7.28 (m, 24 H), 7.57 (m, 16 H) ppm..sup.13C NMR (126 MHz, CDCl.sub.3): δ14.19, 22.39(d, J=17.3 Hz), 29.5 (d, J=8 Hz), 60.59, 128.54(d, J=9 Hz),129.61, 132.85(d, J=28 Hz), 133.38(d, J=12.1 Hz),), 173.23(d, J=17 Hz) ppm..sup.31P {.sup.1H} NMR (203 MHz, CDCl.sub.3): δ-29.69 ppm. IR (neat) v=3056, 2969, 2872, 1727, 1476, 1430, 1369, 1348, 1226, 1163, 1097, 1024, 733, 691 cm.sup.−1. Anal. Calcd for C.sub.64 H.sub.68Cu.sub.4I.sub.4O.sub.4P.sub.4: C, 43.83; H, 4.02. Found: C, 41.76; H, 4.38. ATG : 5% lostof mass at 253° C. DSC : Pf: 128 ° C. recristallization at 61° C.

[0248] This compound has an emission maximum of 560 nm, an excitation maximum of 320 nm and a quantum yield of 99%.

##STR00034##

[0249] .sup.1H NMR (500 MHz, CDCl.sub.3) δ: 7.60 (m, 16 H), 7.32 (m, 24 H), 4.14 (m, 4 H), 3.97 (m, 4 H) , 3.63(m, 12 H) ,3.42 (m, 4 H), 2.58 (m, 16 H), 1.49 (m, 8 H), 1.28 (m, 8 H). .sup.31P NMR (202 MHz, CDCl.sub.3)δ: −30.21(br) .sup.13C NMR (75 MHz, CDCl.sub.3): 6 21.64 (d), 24.96, 27.36, 30.58 (d), 63.46, 69.57, 69.71, 127.50 (d), 128.69, 131.80 (d) 132.33 (d), 172.10 (d)

[0250] This compound has an emission maximum of 560 nm, an excitation maximum of 330 nm and a quantum yield of 52%.

##STR00035##

[0251] .sup.31P NMR (161 MHz, CDCl.sub.3) δ: −31(br) ppm IR (neat) v=3055, 2951, 1730, 1475, 1429, 1218, 1147, 1031, 730, 693.cm.sup.−1

[0252] Conjugates with two different types of ligands were prepared according to the following scheme. The method is according as described above.

##STR00036##

[0253] For example, the following conjugates were obtained:

##STR00037##

[0254] .sup.1H NMR (600 MHz, CDCl.sub.3): δH=1.53 (m, 4 H), 1.69 (m, 4 H), 1.96 (br, 2 H), 2.17 (td, 4 H), 2.58 (m, 8 H), 2.70 (m, 4 H), 2.86 (m, 4 H), 3.11 (d, 4 H), 4.01 (t, 4 H), 4.92 (m, 4 H), 5.77 (m, 2 H), 6.94 (m,2 H), 7.19 (m, 6 H), 7.34 (m, 24 H), 7.63 (m, 16 H) .sup.13C{1H} NMR (75 MHz, CDCl3): δ C=18.10, 22.24 (d), 22.41(d), 24.83, 27.53, 29.46(d), 29.63(d),31.61, 34.57, 64.15, 84.18, 116.24, 122.37, 126.04, 127.30, 128.45 (d), 128.61 (d), 129.71, 129.82, 130.30, 131.87, 132.42 (d), 132.70(d), 133.30 (d), 133.40, 135.76, 148.93, 171.28 (d), 172.98 (d). .sup.31P NMR (161 MHz, CDCl.sub.3)δ: −29.68 (br)

##STR00038##

[0255] .sup.1H NMR (600 MHz, CDCl.sub.3): δH=1.94 (s, 6 H), 2.50 (m, 4 H), 2.63 (m, 8 H), 2.80 (m, 4 H), 3.19 (d, 4 H), 4.98 (m, 4 H), 5.80 (m, 2 H), 6.91 (m, 2 H), 7.16 (m, 6 H), 7.29 (m, 24 H), 7.58 (m, 16 H)

[0256] .sup.13C{1H} NMR (75 MHz, CDCl3): δ C=21.36 (d), 22.71, 29.57(d), 31.64, 34.81, 38.71(d), 116.32, 122.39, 126.10, 127.34, 128.70 (d), 128.90 (d), 129.87, 129.98, 130.34, 131.87, 132.14 (d), 132.65(d), 133.05 (d), 133.15, 135.87, 148.94, 171.27 (d), 207.30 (d).

[0257] .sup.31P NMR (161 MHz, CDCl.sub.3)δ: −30 (br)

##STR00039##

[0258] .sup.1H NMR (600 MHz, CDCl.sub.3): δH=0.94 (m, 12 H), 1.23 (m, 16 H), 1.51 (m, 2 H), 2.56 (m, 8 H), 2.72 (m, 4 H), 2.85 (m, 4 H), 3.16 (d, 4 H), 3.90 (m, 4 H), 4.93 (m, 4 H), 5.77 (m, 2 H), 6.94 (m, 2 H), 7.19 (m, 6 H), 7.34 (m, 24 H), 7.63 (m, 16 H)

[0259] .sup.13C{1H} NMR (75 MHz, CDCl3): δ C=10.93, 14.09, 22.21 (d), 22.34 (d), 22.96, 23.68, 28.87, 29.54 (d), 29.60 (d), 30.29, 34.56, 38.60, 67.29, 116.26, 122.37, 126.03, 127.29, 128.43(d), 128.60 (d), 129.68, 129.81, 130.29, 131.87, 132.41, 132.62, 133.29(d), 133.39 (d), 135.77, 148.93, 171.28 (d), 173.1 (d) .sup.31P NMR (161 MHz, CDCl.sub.3) δ: −29.9 (br)