Long-term stable photoactive composition, such as phosphorescent composition or TTA-photon upconversion composition

Abstract

A long-term stable photoactive composition, namely a phosphorescent composition or a TTA-photon upconversion composition, contains: a) at least one compound, which has a triplet state capable of energy transfer via an emissive process or a non-emissive process, wherein the at least one compound having a triplet state is i) at least one phosphorescent compound and/or ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound and wherein the at least one emissive compound is preferably capable of a triplet-triplet annihilation, and b) at least one compound capable of reacting with singlet oxygen, wherein the at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond and is selected from the group consisting of compounds having anyone of the general formulae (I) to (X).

Claims

1. A composition containing: a) at least one compound capable of reacting with singlet oxygen, and b) at least one compound, which has a triplet state capable of energy transfer via an emissive process or a non-emissive process, wherein the at least one compound having a triplet state is i) at least one phosphorescent compound sufficiently soluble in the compound capable of reacting with singlet oxygen and/or ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound, wherein the at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond and is selected from the group consisting of compounds having anyone of the following general formulae (I) to (X): ##STR00066## wherein X is O or S, R is alkenyl or alkynyl and R1 is H, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00067## wherein X is O or S, R is alkenyl or alkynyl, Y is alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, aralkynyl, aryl or heteroaryl and R1, R2, R3 are independently from each other H, XR, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkenyl, aralkynyl, aralkyl, aryl or heteroaryl, wherein X and R are as defined above, ##STR00068## wherein X is N or P, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00069## wherein PEG is an oligoethylene glycol or polyethylene glycol group having 2 to 99 ethylene glycol units, R1 is alkenyl or alkynyl, Y is Si and R2 and R3 are independently from each other H, COOR, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl or XR4, wherein X is N, P or As and R, R4 are independently from each other alkenyl or alkynyl, ##STR00070## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00071## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00072## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00073## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00074## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1, R2 and R3 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00075## wherein n, m and o are independently from each other an integer between 1 and 20 and p is an integer of 2 or more, ##STR00076## wherein R is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n and m are independently from each other an integer between 1 and 20 and p is an integer of 2 or more or ##STR00077## wherein R and R1 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n is an integer between 1 and 20 and p is an integer of 2 or more, wherein the total concentration of all phosphorescent compounds is 1.Math.10.sup.5 to 1.Math.10.sup.3 mol/l, and wherein the total content of all phosphorescent compounds and all compounds comprising at least one terminal unsaturated carbon-carbon bond in the composition is at least 90 mol-%.

2. A composition containing: a) at least one compound capable of reacting with singlet oxygen, and b) at least one compound, which has a triplet state capable of energy transfer via an emissive process or a non-emissive process, wherein the at least one compound having a triplet state is i) at least one phosphorescent compound sufficiently soluble in the compound capable of reacting with singlet oxygen and/or ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound, wherein the at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond and is selected from the group consisting of compounds having anyone of the following general formulae (I) to (X): ##STR00078## wherein X is O or S, R is alkenyl or alkynyl and R1 is H, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00079## wherein X is O or S, R is alkenyl or alkynyl, Y is alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, aralkynyl, aryl or heteroaryl and R1, R2, R3 are independently from each other H, XR, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkenyl, aralkynyl, aralkyl, aryl or heteroaryl, wherein X and R are as defined above, ##STR00080## wherein X is N or P, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00081## wherein PEG is an oligoethylene glycol or polyethylene glycol group having 2 to 99 ethylene glycol units, R1 is alkenyl or alkynyl, Y is Si and R2 and R3 are independently from each other H, COOR, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl or XR4, wherein X is N, P or As and R, R4 are independently from each other alkenyl or alkynyl, ##STR00082## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00083## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00084## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00085## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00086## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1, R2 and R3 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00087## wherein n, m and o are independently from each other an integer between 1 and 20 and p is an integer of 2 or more, ##STR00088## wherein R is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n and m are independently from each other an integer between 1 and 20 and p is an integer of 2 or more or ##STR00089## wherein R and R1 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n is an integer between 1 and 20 and p is an integer of 2 or more, wherein the total concentration of all sensitizer compounds is 1.Math.10.sup.5 to 1.Math.10.sup.3 mol/l, the total concentration of all emissive compounds is 1.Math.10.sup.2 to 1.Math.10.sup.4 mol/l and the total content of all sensitizer compounds, all emissive compounds and all compounds capable of reacting with singlet oxygen is at least 90 mol-%.

3. A composition containing: a) at least one compound capable of reacting with singlet oxygen, and b) at least one compound, which has a triplet state capable of energy transfer via an emissive process or a non-emissive process, wherein the at least one compound having a triplet state is i) at least one phosphorescent compound sufficiently soluble in the compound capable of reacting with singlet oxygen and/or ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound, wherein the at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond and is selected from the group consisting of compounds having anyone of the following general formulae (I) to (X): ##STR00090## wherein X is O or S, R is alkenyl or alkynyl and R1 is H, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00091## wherein X is O or S, R is alkenyl or alkynyl, Y is alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, aralkynyl, aryl or heteroaryl and R1, R2, R3 are independently from each other H, XR, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkenyl, aralkynyl, aralkyl, aryl or heteroaryl, wherein X and R are as defined above, ##STR00092## wherein X is N or P, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00093## wherein PEG is an oligoethylene glycol or polyethylene glycol group having 2 to 99 ethylene glycol units, R1 is alkenyl or alkynyl, Y is Si and R2 and R3 are independently from each other H, COOR, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl or XR4, wherein X is N, P or As and R, R4 are independently from each other alkenyl or alkynyl, ##STR00094## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00095## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00096## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00097## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00098## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1, R2 and R3 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00099## wherein n, m and o are independently from each other an integer between 1 and 20 and p is an integer of 2 or more, ##STR00100## wherein R is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n and m are independently from each other an integer between 1 and 20 and p is an integer of 2 or more or ##STR00101## wherein R and R1 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n is an integer between 1 and 20 and p is an integer of 2 or more, wherein the at least one compound having a triplet state capable of energy transfer via an emissive process or a non-emissive process is i) at least one phosphorescent compound that can be sufficiently dissolved in the compound capable of reacting with singlet oxygen.

4. A composition containing: a) at least one compound capable of reacting with singlet oxygen, and b) at least one compound, which has a triplet state capable of energy transfer via an emissive process or a non-emissive process, wherein the at least one compound having a triplet state is i) at least one phosphorescent compound sufficiently soluble in the compound capable of reacting with singlet oxygen and/or ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound, wherein the at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond and is selected from the group consisting of compounds having anyone of the following general formulae (I) to (X): ##STR00102## wherein X is O or S, R is alkenyl or alkynyl and R1 is H, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00103## wherein X is O or S, R is alkenyl or alkynyl, Y is alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, aralkynyl, aryl or heteroaryl and R1, R2, R3 are independently from each other H, XR, alkyl, ether-alkyl, ether-alkenyl, alkenyl, alkynyl, aralkenyl, aralkynyl, aralkyl, aryl or heteroaryl, wherein X and R are as defined above, ##STR00104## wherein X is N or P, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00105## wherein PEG is an oligoethylene glycol or polyethylene glycol group having 2 to 99 ethylene glycol units, R1 is alkenyl or alkynyl, Y is Si and R2 and R3 are independently from each other H, COOR, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl or XR4, wherein X is N, P or As and R, R4 are independently from each other alkenyl or alkynyl, ##STR00106## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00107## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00108## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00109## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1 and R2 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00110## wherein X is P, S, B or Si, R is alkenyl or alkynyl and R1, R2 and R3 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, ##STR00111## wherein n, m and o are independently from each other an integer between 1 and 20 and p is an integer of 2 or more, ##STR00112## wherein R is H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n and m are independently from each other an integer between 1 and 20 and p is an integer of 2 or more or ##STR00113## wherein R and R1 are independently from each other H, alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl, n is an integer between 1 and 20 and p is an integer of 2 or more, wherein the at least one compound having a triplet state capable of energy transfer via an emissive process or a non-emissive process is ii) at least one sensitizer compound being capable of absorbing radiation at a first frequency v.sub.1 and at least one emissive compound, wherein the at least one sensitizer compound is capable of transferring energy to the at least one emissive compound and wherein the at least one emissive compound, after obtaining energy transferred from the at least one sensitizer compound, is capable of emitting light at a second frequency v.sub.2, wherein the following equation is fulfilled: v.sub.2>v.sub.1, wherein the at least one sensitizer compound is capable of a triplet-triplet energy transfer to the at least one emissive compound.

5. The composition in accordance with claim 4, wherein the at least one emissive compound is capable of a triplet-triplet annihilation.

6. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen is contained in the composition in such an amount that the number of terminal unsaturated carbon-carbon bonds of the at least one compound capable of reacting with singlet oxygen is at least 100 times higher in the composition than the number of molecules of all compounds having a triplet state capable of energy transfer via an emissive process or a non-emissive process.

7. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (II), in which X is oxygen, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl, Y is C.sub.1-6-alkyl or phenyl and R1, R2, R3 are independently from each other H and XR, wherein X is oxygen and R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

8. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen is selected from the group consisting of 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7-octene-1-ol, 1,2-di-(3-buten-1-yloxy)ethane, 1,2-di-(4-penten-1-yloxy)ethane, 1,2-di-(5-hexen-1-yloxy)ethane, 1,2-di-(6-hepten-1-yloxy)ethane, 1,2-di-(7-octen-1-yloxy)ethane, 1,2-di-(3-buten-1-yloxy)benzene, 1,2-di-(4-penten-1-yloxy)benzene, 1,2-di-(5-hexen-1-yloxy)benzene, 1,2-di-(6-hepten-1-yloxy)benzene, 1,2-di-(7-octen-1-yloxy)benzene, 1,3,5-tri-(3-buten-1-yloxy)benzene, 1,3,5-tri-(4-penten-1-yloxy)benzene, 1,3,5-tri-(5-hexen-1-yloxy)benzene, 1,3,5-tri-(6-hepten-1-yloxy)benzene, 1,3,5-tri-(7-octen-1-yloxy)benzene and arbitrary combinations of two or more of these compounds.

9. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (III), wherein X is phosphorus, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl and R1 and R2 are independently from each other H or selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

10. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (IV), in which PEG is an oligoethylene glycol or polyethylene glycol group having 2 to 99 ethylene glycol units, R1 is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl, Y is Si and R2, R3 are independently from each other H, COOR, XR4 or alkenyl selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl, wherein X is N or P and R, R4 are independently from each other selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

11. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (VII), wherein X is S, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl and R1 is C.sub.3-8-alkyl, phenyl or alkenyl selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

12. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (VI), wherein X is P, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl and R1 and R2 are independently from each other C.sub.3-8-alkyl, phenyl or alkenyl selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

13. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (VIII), wherein X is B, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl and R1 and R2 are independently from each other C.sub.3-8-alkyl, phenyl or alkenyl selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

14. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen has the general formula (IX), wherein X is Si, R is selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl and R1, R2 and R3 are independently from each other C.sub.3-8-alkyl, phenyl or alkenyl selected from the group consisting of allyl, 3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl, 7-octen-1-yl, 8-nonen-1-yl, 9-decen-1-yl and 10-undecen-1-yl.

15. The composition in accordance with claim 4, wherein the at least one compound capable of reacting with singlet oxygen is one according to the general formula (Xa), wherein n, m and o are independently from each other an integer between 1 and 10 and p is an integer of 2 to 120.

16. The composition in accordance with claim 15, wherein the at least one compound capable of reacting with singlet oxygen is one according to the subsequent formulae (XI) to (XIV): ##STR00114## wherein in each of these formulae p is an integer of 2 to 120.

Description

(1) Subsequently, the present invention will be described in more detail by way of non-limiting examples and comparative examples making reference to the figures, wherein:

(2) FIG. 1 is a luminescence spectrum comparing a composition including MF16 (example 1) as singlet oxygen inhibitor with a composition including toluene (comparative example 1) as solvent.

(3) FIG. 2 shows the dependency of the integral UC-fluorescence on the excitation intensity for the compositions of examples 1 and 2 and of comparative example 1.

(4) FIG. 3 is a luminescence spectrum comparing a composition including MF81 (example 2) as singlet oxygen inhibitor with a composition including MF16 (example 1) as solvent.

(5) FIG. 4 is a luminescence spectrum comparing a composition including MF54 (example 5), MF82 (example 6) and MF14 (example 7) as singlet oxygen inhibitor.

(6) FIG. 5 is a phosphorescence spectrum of a composition including MF16 (example 10).

(7) FIG. 6 are phosphorescence spectra for a composition including MF16 (example 10) as singlet oxygen inhibitor at different excitation laser intensities.

(8) FIG. 7 is the .sup.1H-NMR spectrum of the hyperbranched phosphoester of example 11.

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1

(9) (Singlet Oxygen Protection at TTA-UC by an Organophosphate Monomer)

(10) Di-(5-hexen-1-yl) phenyl phosphate (subsequently abbreviated as MF16) was used as singlet oxygen inhibitor in a composition in accordance with the present invention. More specifically, a composition consisting of 1.Math.10.sup.4 mol/l 2,7,8,12,13,17,18-octaethylporphyrin platinum (PtOEP) as sensitizer compound, 2.Math.10.sup.3 mol/l 1,2,3,4-dibenzanthracene (perylene) as emissive compound and MF16 as singlet oxygen inhibitor was prepared.

(11) ##STR00059##

(12) Afterwards, the composition was shaped to a cuboid having a thickness of 400 m. Then, a luminescence spectrum of the sample was recorded at room temperature using an excitation wavelength of 532 nm and an excitation laser intensity of 3.17 W/cm.sup.2 at glove box atmosphere having an oxygen concentration of 2 ppm.

(13) For comparison, a composition according to comparative example 1 was prepared as described above for example 1 except of using toluene instead of MF16. A luminescence spectrum of this sample was recorded under the same conditions described above for example 1. The results are shown in FIG. 1.

(14) As it derives from FIG. 1, the TTA-UC efficiency of the composition of example 1 including MF16 as solvent is comparable with that of the composition of comparative example 1 including toluene, when glove-box atmosphere is used.

(15) Moreover, for both compositions the TTA-UC-fluorescence has been measured in dependency of the excitation intensity in different atmospheres having different oxygen concentrations. The results are shown in FIG. 2. As it derives from FIG. 2, the TTA-UC efficiencies for the composition of example 1 are nearly identical at 2 ppm oxygen concentration and at 21% oxygen concentration and are higher than that of the composition of comparative example 2 at glove-box conditions, i.e. in an atmosphere with 2 ppm oxygen concentration.

EXAMPLE 2

(16) (Singlet Oxygen Protection at TTA-UC by an Organophosphate Monomer)

(17) Example 1 was repeated except of using as singlet oxygen inhibitor tri-(5-hexen-1-yl) phosphate (MF81) instead of MF16.

(18) ##STR00060##

(19) The composition of example 2 was evaluated as described above for the composition of example 1 in comparison to that of the comparative example 1 except that the luminescence spectrum was recorded in ambient atmosphere with an oxygen concentration of 21%.

(20) The results are shown in FIGS. 2 and 3.

(21) As it derives from FIG. 3, the TTA-UC efficiency of the composition of example 2 including MF81 as solvent is as high as for MF16 (example 1) and thus much higher than that of the composition of comparative example 1 including toluene. Moreover, the TTA-UC efficiencies for the composition of example 2 are nearly identical at 2 ppm oxygen concentration and at 21% oxygen concentration and are higher than that of the composition of comparative example 2 at glove-box atmosphere, i.e. at 2 ppm oxygen concentration.

EXAMPLES 3 AND 4

(22) (Singlet Oxygen Protection at TTA-UC by an Organophosphate Monomer)

(23) Example 2 was repeated except that as sensitizer and emissive compounds PdTBP and Y805 for example 3 and PdTNP and Y808 for example 4 were used.

(24) ##STR00061## ##STR00062##

(25) A luminescence spectrum of the samples were recorded at room temperature using an excitation wavelength of 532 nm and an excitation laser intensity of 3.17 W/cm.sup.2 in atmospheres having oxygen concentrations of 2 ppm and 21% for example 3 and in an atmospheres having an oxygen concentration of 21% for example 4.

(26) Similar good results were obtained as for examples 1 and 2. This shows that the advantageous properties of the composition in accordance with the present patent application are due to the addition of the singlet oxygen inhibitor comprising at least one terminal unsaturated carbon-carbon bond and are achieved for different sensitizer and emissive compounds.

EXAMPLES 5 TO 7

(27) (Singlet Oxygen Protection at TTA-UC by Hyperbranched Polyphosphoesters)

(28) Example 1 was repeated except that three different hyperbranched polyphosphoesters according to the following formulae were used as singlet oxygen inhibitor:

(29) ##STR00063##

(30) A luminescence spectrum of the samples were recorded at room temperature using an excitation wavelength of 532 nm and an excitation laser intensity of 3.17 W/cm.sup.2 in ambient atmosphere having an oxygen concentration of 21%. The results are shown in FIG. 4. Similar good results were obtained as for examples 1 to 4.

EXAMPLES 8 AND 9

(31) (Singlet Oxygen Protection at TTA-UC by Alcohol and Silicate)

(32) Example 1 was repeated except that the following two compounds were used as singlet oxygen inhibitor:

(33) ##STR00064##

(34) A luminescence spectrum of the samples were recorded at room temperature using an excitation wavelength of 532 nm and an excitation laser intensity of 3.17 W/cm.sup.2 in atmospheres having oxygen concentrations of 2 ppm and of 21%. Similar good results were obtained as for examples 1 to 7.

EXAMPLE 10 AND COMPARATIVE EXAMPLE 2

(35) (Singlet Oxygen Protection at Phosphorescence by an Organophosphate Monomer)

(36) A phosphorescent composition consisting of 1.Math.10.sup.4 mol/l PtOEP as sensitizer/phosphorescent compound and MF16 as singlet oxygen inhibitor was prepared (example 10).

(37) Afterwards, the composition was shaped to a cuboid having a thickness of 400 m. Then, a phosphorescence spectrum of the sample was recorded at room temperature using an excitation wavelength of 532 nm at different excitation laser intensities in ambient atmosphere with an oxygen content of 21%.

(38) For comparison, a composition according to comparative example 2 was prepared as described above for example 10 except of using toluene instead of MF16. Phosphorescence spectra of this sample were recorded under the conditions described above for example 10. The results are shown in FIGS. 5 and 6.

(39) As it derives from FIGS. 5 and 6, the process of phosphorescence of metallated macrocycles is effectively protected for long temporal period from quenching by oxygen independent from the excitation laser intensity, when using at least one compound capable of reacting with singlet oxygen comprises at least one terminal unsaturated carbon-carbon bond.

EXAMPLE 11

(40) (Determination of Number of Terminal Carbon-Carbon Double Bonds in a Hyperbranched Phosphoester)

(41) The following hyperbranched phosphoester was prepared.

(42) ##STR00065##

(43) Afterwards, the number average molecular weight of the phosphoester was determined with GPC as described above as being 4,500 g/mol. Moreover, it was confirmed by SEC analysis that no monomers were present in the system. Then, a .sup.1H-NMR spectrum was recorded, which is shown in FIG. 7. In this spectrum, the ratio of the signal intensities for terminal and the internal double bonds was 1:1.

(44) It follows from these results that the polymer has a polymerization degree of 20 and that it carries 20 terminal carbon-carbon double bonds.