Liquid crystalline medium

Abstract

The present invention relates to benzotriazole derivatives selected from the group of compounds of formulae Ia, Ib and Ic as defined in claim 1, to mesogenic media comprising the compounds of formulae Ia, Ib and Ic, and to the use of these compounds and mesogenic media in optical, electronic and electro-optical applications, in particular in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Claims

1. A mesogenic medium comprising one or more compounds selected from the group of compounds of formulae Ia, Ib and Ic ##STR00408## wherein R.sup.11, R.sup.12, R.sup.13 identically or differently, denote H, F, CN, CO, N(R.sup.z).sub.2, SO.sub.2R.sup.z, ##STR00409## CH═C(CN).sub.2, or a straight-chain alkyl having 1 to 20 C atoms, or branched or cyclic alkyl having 3 to 20 C atoms, in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —C(R.sup.z)═C(R.sup.z)—, —C≡C—, ##STR00410## —N(R.sup.z)—, —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, Br, I or CN, R.sup.z on each occurrence, identically or differently, denotes H, halogen, a straight-chain alkyl having 1 to 12 C atoms, or branched or cyclic alkyl having 3 to 12 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by —O, S, CO, CO O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F or Cl, A.sup.11, A.sup.12 each, independently of one another, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, A.sup.21, A.sup.22 on each occurrence, identically or differently, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, or a cyclic alkyl group having 3 to 10 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by O, L on each occurrence, identically or differently, denotes F, Cl, CN, OH, SCN, SF.sub.5 or a straight-chain, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms, X is S, Se or Te, Z.sup.11, Z.sup.12 on each occurrence, identically or differently, denote a single bond, —CR.sup.x1═CR.sup.x2—, —C(O)—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.21, Z.sup.22 on each occurrence, identically or differently, denote a single bond, —O—, —S—, —C(O)—, —CR.sup.y1R.sup.y2—, —CF.sub.2O—, —OCF.sub.2—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2S—, —SCF.sub.2—, —(CH.sub.2).sub.n1—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —(CF.sub.2).sub.n1—, —CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.31, Z.sup.32 on each occurrence, identically or differently, denote a single bond, —O—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2—, —CF.sub.2CF.sub.2— or —C(O)—, R.sup.x1, R.sup.x2 independently of one another, denote H, F, Cl, CN or alkyl having 1 to 12 C atoms, R.sup.y1 denotes H or alkyl having 1 to 12 C atoms, R.sup.y2 denotes alkyl having 1 to 12 C atoms, n1 denotes 1, 2, 3 or 4, and r, s independently of one another, denote 0, 1, 2 or 3.

2. The mesogenic medium according to claim 1, wherein A.sup.11 and A.sup.12 denote, independently of one another, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl or thienothiophene-2,5-diyl, wherein one or more H atoms may be replaced by the group L.

3. The mesogenic medium according to claim 1, wherein Z.sup.11 and Z.sup.12 denote a single bond.

4. The mesogenic medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae CY, PY and AC ##STR00411## AC wherein ##STR00412## denotes ##STR00413## and ##STR00414## denote ##STR00415## denotes ##STR00416## R.sup.1, R.sup.2, R.sup.AC1, R.sup.AC2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO—, or —COO— in such a way that O atoms are not linked directly to one another, Z.sup.x, Z.sup.y, Z.sup.AC each, independently of one another, denote —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CO—O—, —O—CO—, —C.sub.2F.sub.4—, —CF═CF—, —CH═CH—CH.sub.2O— or a single bond, L.sup.1, L.sup.2, L.sup.3, L.sup.4 each, independently of one another, denote F, Cl, CN, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, or CHF.sub.2, a is 1 or 2, b is 0 or 1, c is 0, 1 or 2, and d is 0 or 1.

5. The mesogenic medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae II to VIII ##STR00417## wherein ##STR00418## each, independently of one another, denote ##STR00419## R.sup.20 identically or differently, denotes a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CF.sub.2O—, —CH═CH—, ##STR00420## —O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, X.sup.20 identically or differently, denotes F, Cl, CN, SF.sub.5, SCN, NCS, a halogenated alkyl radical, a halogenated alkenyl radical, a halogenated alkoxy radical or a halogenated alkenyloxy radical, each having 1 to 6 C atoms, Y.sup.20, Y.sup.21, Y.sup.22, Y.sup.23, Y.sup.24 each, identically or differently, denote H or F, Z.sup.20 denotes —C.sub.2H.sub.4—, —(CH.sub.2).sub.4—, —CH═CH—, —CF═CF—, —C.sub.2F.sub.4—, —CH.sub.2CF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —COO— or —OCF.sub.2—, in formulae V and VI also a single bond, in formulae V and VIII also —CF.sub.2O—, r denotes 0 or 1, and s denotes 0 or 1.

6. The mesogenic medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK and O ##STR00421## wherein R.sup.5, R.sup.6, R.sup.O1 and R.sup.O2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO—, or —COO— in such a way that O atoms are not linked directly to one another, ##STR00422## denotes ##STR00423## denotes ##STR00424## denotes ##STR00425## and ##STR00426## denotes ##STR00427## Z.sup.O1 denotes —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, —C═C— or a single bond, Z.sup.O2 denotes CH.sub.2O, —C(O)O—, —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, or a single bond, o is 1 or 2, and e is 1 or 2.

7. The mesogenic medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae O3 to O5 ##STR00428## wherein R.sup.O1 and R.sup.O2, identically or differently, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.

8. The mesogenic medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK1 to DK12: ##STR00429## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2 to 6 C atoms.

9. A device for regulating the passage of energy from an outside space into an inside space, wherein the device contains a switching layer comprising the mesogenic medium according to claim 1.

10. A window comprising the device according to claim 9.

11. An electro-optical display, a device for regulating the passage of energy from an outside space into an inside space, an electrical semiconductor, an organic field-effect transistor, a printed circuit, a radio frequency identification element, an organic light-emitting diode, a lighting element, a photovoltaic device, an optical sensor, an effect pigment, a decorative element or as a dye for colouring polymers, comprising the mesogenic medium according to claim 1.

12. A mesogenic medium comprising one or more compounds of formula Ia ##STR00430## wherein R.sup.11, R.sup.12, R.sup.13 identically or differently, denote H, F, CN, CO, N(R.sup.z).sub.2, SO.sub.2R.sup.z, ##STR00431## CH═C(CN).sub.2, or a straight-chain alkyl having 1 to 20 C atoms, or branched or cyclic alkyl having 3 to 20 C atoms, in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —C(R.sup.z)═C(R.sup.z)—, —C≡C—, ##STR00432## —N(R.sup.z)—, —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, Br, I or CN,  wherein at least one of R.sup.11, R.sup.12 and R.sup.13 is ##STR00433## R.sup.z on each occurrence, identically or differently, denotes H, halogen, a straight-chain alkyl having 1 to 12 C atoms, or branched or cyclic alkyl having 3 to 12 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by —O, S, CO, CO O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F or Cl, A.sup.11, A.sup.12 each, independently of one another, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, A.sup.21, A.sup.22 on each occurrence, identically or differently, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, or a cyclic alkyl group having 3 to 10 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by O, L on each occurrence, identically or differently, denotes F, Cl, CN, OH, SCN, SF.sub.5 or a straight-chain, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms, X is S, Se or Te, Z.sup.11, Z.sup.12 on each occurrence, identically or differently, denote a single bond, —CR.sup.x1═CR.sup.x2—, —C(O)—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.21, Z.sup.22 on each occurrence, identically or differently, denote a single bond, —O—, —S—, —C(O)—, —CR.sup.y1R.sup.y2—, —CF.sub.2O—, —OCF.sub.2—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2S—, —SCF.sub.2—, —(CH.sub.2).sub.n1—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —(CF.sub.2).sub.n1—, —CR.sup.x1═CR.sup.x2—, —C≡C—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.31, Z.sup.32 on each occurrence, identically or differently, denote a single bond, —O—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2—, —CF.sub.2CF.sub.2— or —C(O)—, R.sup.x1, R.sup.x2 independently of one another, denote H, F, Cl, CN or alkyl having 1 to 12 C atoms, R.sup.y1 denotes H or alkyl having 1 to 12 C atoms, R.sup.y2 denotes alkyl having 1 to 12 C atoms, n1 denotes 1, 2, 3 or 4, and r, s independently of one another, denote 0, 1, 2 or 3.

13. The mesogenic medium according to claim 12, wherein A.sup.11 and A.sup.12 denote, independently of one another, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl or thienothiophene-2,5-diyl, wherein one or more H atoms may be replaced by the group L.

14. The mesogenic medium according to claim 12, wherein Z.sup.11 and Z.sup.12 denote a single bond.

15. The mesogenic medium according to claim 12, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae CY, PY and AC ##STR00434## wherein ##STR00435## denotes ##STR00436## and ##STR00437## denote ##STR00438## denotes ##STR00439## R.sup.1, R.sup.2 R.sup.AC1, R.sup.AC2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO—, or —COO— in such a way that O atoms are not linked directly to one another, Z.sub.x, Z.sup.y, Z.sup.AC each, independently of one another, denote —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CO—O—, —O—CO—, —C.sub.2F.sub.4—, —CF═CF—, —CH═CH—CH.sub.2O— or a single bond, L.sup.1, L.sup.2, L.sup.3, L.sup.4 each, independently of one another, denote F, Cl, CN, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, or CHF.sub.2, a is 1 or 2, b is 0 or 1, c is 0, 1 or 2, and d is 0 or 1.

16. The mesogenic medium according to claim 12, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae II to VIII ##STR00440## wherein ##STR00441## each, independently of one another, denote ##STR00442## R.sup.20 identically or differently, denotes a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CF.sub.2O—, —CH═CH—, ##STR00443## —O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, X.sup.20 identically or differently, denotes F, Cl, CN, SF.sub.5, SCN, NCS, a halogenated alkyl radical, a halogenated alkenyl radical, a halogenated alkoxy radical or a halogenated alkenyloxy radical, each having 1 to 6 C atoms, Y.sup.20, Y.sup.21, Y.sup.22, Y.sup.23, Y.sup.24 each, identically or differently, denote H or F, Z.sup.20 denotes —C.sub.2H.sub.4—, —(CH.sub.2).sub.4—, —CH═CH—, —CF═CF—, —C.sub.2F.sub.4—, —CH.sub.2CF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —COO— or —OCF.sub.2—, in formulae V and VI also a single bond, in formulae V and VIII also —CF.sub.2O—, r denotes 0 or 1, and s denotes 0 or 1.

17. The mesogenic medium according to claim 12, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK and 0 ##STR00444## wherein R.sup.5, R.sup.6, R.sup.O1 and R.sup.O2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO—, or —COO— in such a way that O atoms are not linked directly to one another, ##STR00445## denotes ##STR00446## denotes ##STR00447## denotes ##STR00448## and ##STR00449## denotes ##STR00450## Z.sup.O1 denotes —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, —C═C— or a single bond, Z.sup.O2 denotes CH.sub.2O, —C(O)O—, —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, or a single bond, o is 1 or 2, and e is 1 or 2.

18. The mesogenic medium according to claim 12, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae O3 to O5 ##STR00451## wherein R.sup.O1 and R.sup.O2, identically or differently, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.

19. The mesogenic medium according to claim 12, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK1 to DK12: ##STR00452## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2 to 6 C atoms.

20. A device for regulating the passage of energy from an outside space into an inside space, wherein the device contains a switching layer comprising the mesogenic medium according to claim 12.

21. A window comprising the device according to claim 20.

22. An electro-optical display, a device for regulating the passage of energy from an outside space into an inside space, an electrical semiconductor, an organic field-effect transistor, a printed circuit, a radio frequency identification element, an organic light-emitting diode, a lighting element, a photovoltaic device, an optical sensor, an effect pigment, a decorative element or as a dye for colouring polymers, comprising the mesogenic medium according to claim 12.

23. A compound of formula Ia ##STR00453## wherein R.sup.11, R.sup.12, R.sup.13 identically or differently, denote H, F, CN, CO, N(R.sup.z).sub.2, SO.sub.2R.sup.z, ##STR00454## CH═C(CN).sub.2, or a straight-chain alkyl having 1 to 20 C atoms, or branched or cyclic alkyl having 3 to 20 C atoms, in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —C(R.sup.z)═C(R.sup.z)—, —C≡C—, ##STR00455## —N(R.sup.z)—, —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, Br, I or CN,  wherein at least one of R.sup.11, R.sup.12 and R.sup.13 is ##STR00456## R.sup.z on each occurrence, identically or differently, denotes H, halogen, a straight-chain alkyl having 1 to 12 C atoms, or branched or cyclic alkyl having 3 to 12 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by —O, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F or Cl, A.sup.11, A.sup.12 each, independently of one another, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, A.sup.21, A.sup.22 on each occurrence, identically or differently, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, or a cyclic alkyl group having 3 to 10 C atoms, in which one or more non-adjacent CH.sub.2 groups may be replaced by O, L on each occurrence, identically or differently, denotes F, Cl, CN, OH, SCN, SF.sub.5 or a straight-chain, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms X is S, Se or Te, Z.sup.11, Z.sup.12 on each occurrence, identically or differently, denote a single bond, —CR.sup.x1═CR.sup.x2—, —C(O)—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.21, Z.sup.22 on each occurrence, identically or differently, denote a single bond, —O—, —S—, —C(O)—, —CR.sup.y1R.sup.y2—, —CF.sub.2O—, —OCF.sub.2—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2S—, —SCF.sub.2—, —(CH.sub.2).sub.n1—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —(CF.sub.2).sub.n1—, —CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.31, Z.sup.32 on each occurrence, identically or differently, denote a single bond, —O—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2—, —CF.sub.2CF.sub.2— or —C(O)—, R.sup.x1, R.sup.x2 independently of one another, denote H, F, Cl, CN or alkyl having 1 to 12 C atoms, R.sup.y1 denotes H or alkyl having 1 to 12 C atoms, R.sup.y2 denotes alkyl having 1 to 12 C atoms, n1 denotes 1, 2, 3 or 4, and r, s independently of one another, denote 0, 1, 2 or 3.

24. The compound according to claim 23, wherein the compound exhibits an absorption maximum at a wavelength of greater than 600 nm.

25. The compound according to claim 23, wherein X is S, Z.sup.11, Z.sup.12 denote a single bond, A.sup.11, A.sup.12 denote, independently of one another, 1,4-phenylene, thiophene-2,5-diyl or thienothiophene-2,5-diyl, wherein one or more H atoms may be replaced by the group L, and r, s independently of one another, denote 0, 1 or 2.

26. A method for preparing a compound of formula Ia according to claim 23, comprising subjecting a compound of formula I-SM to a chemical reaction ##STR00457## wherein X is S, Se or Te, and Y is NO.sub.2 or halogen.

Description

EXAMPLES

(1) In the Examples, V.sub.o denotes threshold voltage, capacitive [V] at 20° C., n.sub.e denotes extraordinary refractive index at 20° C. and 589 nm, n.sub.o denotes ordinary refractive index at 20° C. and 589 nm, Δn denotes optical anisotropy at 20° C. and 589 nm, ε∥ denotes dielectric permittivity parallel to the director at 20° C. and 1 kHz, Δ⊥ denotes dielectric permittivity perpendicular to the director at 20° C. and 1 kHz, Δε denotes dielectric anisotropy at 20° C. and 1 kHz, cl.p., T(N,I) denotes clearing point [° C.], γ.sub.1 denotes rotational viscosity measured at 20° C. [mPa.Math.s], determined by the rotation method in a magnetic field, K.sub.1 denotes elastic constant, “splay” deformation at 20° C. [pN], K.sub.2 denotes elastic constant, “twist” deformation at 20° C. [pN], K.sub.3 denotes elastic constant, “bend” deformation at 20° C. [pN],

(2) The term “threshold voltage” for the present invention relates to the capacitive threshold (V.sub.0), unless explicitly indicated otherwise. In the Examples, as is generally usual, the optical threshold can also be indicated for 10% relative contrast (V.sub.10).

Synthesis Examples

(3) Compounds 1 to 9 are prepared according to the following scheme.

(4) ##STR00398##

Synthesis Example 1

Preparation of 5,6-dinitrobenzo[2,1,3]benzothiadiazole (Compound 1)

(5) The precursors for compound 1 are prepared according to methods known in the art, see e.g. G. W. H. Cheeseman, Quinoxalines and Related Compounds. Part VI, 1962, 1170-1176.

(6) A 1 l four-necked apparatus with a stirrer and a thermometer is charged with 15.00 g of 4,5-dinitro-1,2-phenylenediamine (55.3 mmol) in 125 ml of dichloromethane under a nitrogen atmosphere and cooled to −10° C. Then 30.00 ml of triethylamine (221 mmol) and 8.00 ml of thionyl chloride (110 mmol) are consecutively added dropwise, wherein the temperature does not exceed 10° C. The mixture is slowly warmed up to room temperature and then stirred for 20 h. The reaction solution is added to 200 ml of ice water, chloroform (300 ml) is added, and the phases are separated. The aqueous phase is extracted once with chloroform, the combined organic phases are washed once with water, dried over sodium sulphate and filtered, and the solvent is removed under reduced pressure. The residue is subjected to chromatography over silica gel using toluene and then recrystallized from 100 ml of heptane/toluene (3:1) and dried under vacuum. The product is obtained as beige-coloured crystals.

Synthesis Example 2

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-5,6-dinitrobenzo[2,1,3]thiadiazol (Compound 2)

(7) A 250 ml brown glass four-necked apparatus with a stirrer, a thermometer and a reflux condenser is charged with 2.00 g of 5,6-dinitrobenzo[2,1,3]benzothiadiazole (8.44 mmol), 6.30 g of 2-bromo-5-(2-ethylhexyl)-thieno[3,2-b]thienothiophene (18.6 mmol), 3.50 g of potassium carbonate (25.3 mmol), 862 mg of pivalic acid (8.44 mmol) and 423 mg of di-tert-butylmethylphosphoniumtetrafluoroborate [(t-Bu).sub.2MeP*BF.sub.4] (1.70 mmol) in 60 ml of toluene under a nitrogen atmosphere. Then 190 mg of palladium(II) acetate (0.84 mmol) are added, and the mixture is heated under reflux for 20 h. Then the reaction solution is cooled to room temperature, 20 ml of dichloromethane are added, and filtration using a thin layer of celite is carried out. The filtrate is concentrated under reduced pressure. The crude product is subjected to chromatography over silica gel using toluene/heptane (1:2). The product is obtained as a red oil.

Synthesis Example 3

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-benzo[2,1,3]thiadiazole-5,6-diamine (Compound 3)

(8) In a reaction vessel 1.65 g of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-5,6-dinitro-benzo[2,1,3]thiadiazole (Compound 2, 2.07 mmol) are dissolved in 50 ml tetrahydrofuran, 1.00 g of Raney nickel are added and hydrogen is introduced. After 6 h a further 1.00 g of Raney nickel is added and stirring for another 17 h at room temperature is continued, wherein in total 188 ml of hydrogen are used. The reaction mixture is then filtered and the residue is washed with tetrahydrofuran. The solvent is removed from the combined filtrate under reduced pressure. The product is obtained is a yellowish brown solid.

Synthesis Example 4

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (Compound 4)

(9) ##STR00399##

(10) A 25 ml two-necked flask is charged under a nitrogen atmosphere with 350 mg of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-5,6-diaminobenzo[2,1,3]thiadiazole (0.52 mmol) in 3 ml concentrated acetic acid and 3 ml tetrahydrofuran. Then 40 mg of sodium nitrite (0.58 mmol) in 2 ml are slowly added dropwise. The mixture is stirred for 1.5 h at room temperature, wherein a dark solid precipitates. Then 20 ml of water are added, the mixture is cooled to 0° C., and the precipitate is filtered and dried. The crude product is subjected to chromatography over silica gel using toluene and then recrystallized from 15 ml of heptane/toluene (1:2). The product is obtained as a dark blue solid.

(11) The product exhibits an absorption maximum at 635 nm with an average extinction coefficient of 450 [%*cm] and only minimal fluorescence. The degree of anisotropy R as determined in Host Mixture H-1 as given below is 0.70.

Synthesis Example 5

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2-heptyl-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (Compound 5)

(12) ##STR00400##

(13) A 50 ml two-necked flask is charged under a nitrogen atmosphere with 500 mg of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (0.74 mmol) in 15 ml dimethylformamide. Then 0.12 ml of triethylamine (0.84 mmol) is added dropwise. The mixture is stirred for 1 h at room temperature, then 0.13 ml of 1-bromoheptane (0.84 mmol) is added dropwise and stirring at room temperature is continued for 20 h. Then 20 ml of water and 10 ml of dichloromethane are added, and the phases are separated. The aqueous phase is extracted twice with 20 ml dichloromethane. The combined organic phases are washed twice with 50 ml water, dried over sodium sulphate and filtered, and the solvent is removed under reduced pressure. The crude product is subjected twice to chromatography over silica gel using heptane/toluene (4:1) and then recrystallized from 10 ml of heptane. The product is obtained as blue-black needle-shaped crystals.

(14) The product exhibits an absorption maximum at 720 nm with an average extinction coefficient of 450 [%*cm] and only minimal fluorescence. The degree of anisotropy R as determined in Host Mixture H-1 as given below is 0.67.

Synthesis Example 6

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2-triflyl-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (Compound 6)

(15) A 25 ml two-necked flask is charged under a nitrogen atmosphere with 500 mg of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (0.74 mmol) in 4.7 ml of dichloromethane, and the mixture is cooled to 0° C. Then 0.14 ml of triethylamine (1.03 mmol) and 1.80 mg of 4-(dimethylamino)pyridine (0.01 mmol) are added dropwise. The mixture is stirred for 15 minutes, and then 0.17 ml of trifluoromethanesulfonic anhydride (1.03 mmol) is added dropwise, wherein the mixture immediately changes to a green colour. The cooling is stopped and the mixture is stirred at room temperature for 20 h. Then 20 ml of water and 10 ml of dichloromethane are added to the reaction solution, the phases are separated, and the aqueous phase is extracted twice with 20 ml dichloromethane. The combined organic phases are washed twice with 50 ml water, dried over sodium sulphate and filtered, and the solvent is removed under reduced pressure. The crude product is recrystallized from 15 ml of heptane/chlorobutane (2:1). The product is obtained as dark green residue.

(16) The product exhibits an absorption maximum at 844 nm and only minimal fluorescence.

Synthesis Example 7

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2-(1,3,3,4,4,5,5-heptafluoro-2-cyclopentenyl)-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (Compound 7)

(17) A 50 ml two-necked flask is charged under a nitrogen atmosphere with 200 mg of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (0.29 mmol) in 2.2 ml dimethylformamide, and the mixture is cooled to 0° C. Then 17.7 mg of sodium hydride (60% suspension in paraffin oil, 0.44 mmol) are added in portions and the mixture is stirred for 30 minutes. Then 81.3 mg of 1,2,3,3,4,4,5,5-octafluorocyclopentene (0.38 mmol) in 1 ml dimethylformamide are added dropwise, wherein the mixture changed to a green colour. The cooling is stopped and the mixture is stirred at room temperature for 20 h. Then 20 ml of a saturated ammonium chloride solution are added to the reaction mixture. 10 ml of methyl tert-butyl ether are added, the phases are separated, and the aqueous phase is extracted twice with 20 ml methyl tert-butyl ether. The combined organic phases are washed twice with 50 ml water, dried over sodium sulphate and filtered, and the solvent is removed under reduced pressure. The crude product is subjected to chromatography over silica gel using heptane/toluene (1:1) and then to chromatography over silica gel using heptane/toluene (4:1). The product is obtained as a dark green oil.

(18) The product exhibits an absorption maximum at 724 nm and only minimal fluorescence.

Synthesis Example 8

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2-cyano-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazol (Compound 8)

(19) ##STR00401##

(20) A 50 ml two-necked flask is charged under a nitrogen atmosphere with 1.00 g of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (1.47 mmol) in 11.5 ml dimethylformamide. Then 0.23 ml of triethylamine (1.68 mmol) are added dropwise. The mixture is stirred for 1 h, and then 156 mg of cyanogen bromide (1.47 mmol) is added. The mixture is stirred at room temperature for 20 h. 50 ml of water are added, and the precipitating solid is filtered, washed with water and dried. The crude product is subjected to chromatography over silica gel using heptane/toluene (4:1) and then recrystallized from 15 ml of heptane/toluene (9:1). The product is obtained as a dark, almost black solid.

(21) The product exhibits an absorption maximum at 612 nm with an average extinction coefficient of 277 [%*cm] and only minimal fluorescence. The degree of anisotropy R as determined in Host Mixture H-2 as given below is 0.73.

Synthesis Example 9

Preparation of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2-trifluoromethyl-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (Compound 9)

(22) A 50 ml two-necked flask is charged under a nitrogen atmosphere with 500 mg of 4,7-bis-[5-(2-ethylhexyl)-thieno[3,2-b]thiophen-2-yl]-2H-benzo[d]-[1,2,3]-triazolo-[2,1,3]-thiadiazole (0.74 mmol) and 267 mg of 3,3-dimethyl-1-(trifluoromethyl)-1,2-benziodoxole (0.81 mmol) in 10 ml dichloroethane. Then 21 mg of bis(trifluoromethanesulfonyl)amine (0.07 mmol) in 1 ml dichlorethane are added dropwise. The mixture is heated to 60° C. and stirred for 3.5 h auf 60° C. The mixture is then cooled to room temperature, and the solvent is removed under reduce pressure. The crude product is subjected to chromatography over silica gel using heptane/toluene (4:1) and then recrystallized from 15 ml of heptane/toluene (9:1). The product is obtained a dark blue solid.

(23) The product exhibits an absorption maximum at 610 nm and only minimal fluorescence.

Synthesis Examples 10, 11, 12, 13 and 14

(24) In an analogy to the Synthesis Examples 1 to 9 above, Compounds 10 to 14 are prepared according to the following scheme, wherein Ar has the meaning as given in the Synthesis Examples 1 to 9.

(25) ##STR00402##

Synthesis Examples 15 to 22

(26) In accordance with Synthesis Examples 2 to 9, compounds are prepared wherein for Ar—Br 2-bromo-5-[4-(2-ethylhexyl)phenyl]thiophene is used instead of 2-bromo-5-(2-ethylhexyl)-thieno[3,2-b]thienothiophene.

Use Examples

(27) The dyes prepared are investigated with respect to their physical properties and their suitability for use in devices for regulating energy transmission.

Reference Example 1

(28) A liquid-crystal base mixture B-1 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(29) TABLE-US-00007 CPG-3-F 5.00% clearing point [° C.]: 114.5 CPG-5-F 5.00% Δn [589 nm, 20° C.]: 0.135 CPU-3-F 15.00% n.sub.e [589 nm, 20° C.]: 1.63 CPU-5-F 15.00% Δε [1 kHz, 20° C.]: 11.3 CP-3-N 16.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.2 CP-5-N 16.00% K.sub.1 [pN, 20° C.]: 13.4 CCGU-3-F 7.00% K.sub.3 [pN, 20° C.]: 18.5 CBC-33F 4.00% V.sub.0 [V, 20° C.]: 1.15 CBC-53F 4.00% CBC-55F 4.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 3.00% Σ 100.00%

(30) A host mixture H-1 is prepared by mixing 99.97% of mixture B-1 with 0.03% of the compound of formula

(31) ##STR00403##

Examples 1, 2, 3 and 4

(32) The following mixtures M-1, M-2, M-3 and M-4 are prepared based on the host mixture H-1, wherein the following dichroic dye compounds are added according to the following Table and wherein BT-1 and BT-2 are compounds of formula BT-1 and respectively BT-2 as given above.

(33) TABLE-US-00008 M-1 M-2 M-3 M-4 H-1 98.716% 98.365% 98.024% 97.290% BT-1  0.167%  0.250%  0.066%  0.093% BT-2  0.261%  0.310%  0.464%  0.608% Compound 4  0.039%  0.119%  0.473%  0.915% Compound 5  0.412%  0.345%  0.973%  1.094% Compound 8  0.405%  0.611% — —

(34) The mixtures M-1, M-2, M-3 and M-4 are respectively filled into electrically switchable devices having a double cell set-up where the switching layers have a thickness of 25 μm and the performance for the bright state and the dark state are evaluated. Measurements are performed according to norm EN410.

(35) TABLE-US-00009 M-1 M-2 M-3 M-4 light transmittance 10% 4.5% 10%  5% τ.sub.v (dark state) light transmittance 56%  47% 51% 40% τ.sub.v (bright state) solar direct transmittance 44%  41% 40% 38% τ.sub.e (dark state) solar direct transmittance 68%  64% 58% 52% τ.sub.e (bright state) chromaticity coordinate x 0.312 0.313 0.313 0.313 (dark state) chromaticity coordinate y 0.328 0.329 0.329 0.329 (dark state) chromaticity coordinate x 0.317 0.320 0.303 0.299 (bright state) chromaticity coordinate y 0.335 0.337 0.337 0.340 (bright state)

(36) The mixtures M-1, M-2, M-3 and M-4 are well suited for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Reference Example 2

(37) A liquid-crystal host mixture H-2 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(38) TABLE-US-00010 CPG-3-F 8.00% clearing point [° C.]: 114 CPG-5-F 8.00% Δn [589 nm, 20° C.]: 0.130 CPU-5-F 14.00% n.sub.e [589 nm, 20° C.]: 1.62 CPU-7-F 11.00% Δε [1 kHz, 20° C.]: 10.0 CP-5-N 18.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.0 CP-7-N 13.00% CCGU-3-F 7.00% CC-3-O3 2.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 3.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00%

Reference Example 3

(39) A mixture H-3 is prepared by mixing 99.92% of mixture H-2 as described in Reference Example 2 above with 0.05% of the compound of formula S-811 as described in Table F above and with 0.03% of the compound of formula

(40) ##STR00404##

Reference Example 4

(41) A mixture H-4 is prepared by mixing 99.80% of mixture H-2 as described in Reference Example 2 above with 0.10% of the compound of formula

(42) ##STR00405##
and 0.10% of the compound of formula

(43) ##STR00406##

Reference Example 5

(44) A liquid-crystal base mixture B-5 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(45) TABLE-US-00011 CY-3-O2 9.00% clearing point [° C.]: 110.5 CY-3-O4 9.00% Δn [589 nm, 20° C.]: 0.132 CY-5-O2 12.00% n.sub.e [589 nm, 20° C.]: 1.62 CY-5-O4 8.00% Δε [1 kHz, 20° C.]: −4.9 CCY-3-O2 5.00% ε.sub.⊥ [1 kHz, 20° C.]: 8.8 CCY-3-O3 5.00% K.sub.1 [pN, 20° C.]: 16.8 CCY-4-O2 5.00% K.sub.3 [pN, 20° C.]: 20.4 CPY-2-O2 7.00% V.sub.0 [V, 20° C.]: 2.14 CPY-3-O2 6.00% PYP-2-3 12.00% CCP-V-1 6.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CBC-33F 5.00% CBC-53F 5.00% Σ 100.00%

(46) A host mixture H-5 is prepared by mixing 99.97% of mixture B-5 with 0.03% of the compound of formula

(47) ##STR00407##

Reference Example 6

(48) A liquid-crystal host mixture H-6 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(49) TABLE-US-00012 CY-3-O4 25.00% clearing point [° C.]: 75.4 CCY-3-O2 6.00% Δn [589 nm, 20° C.]: 0.100 CCY-3-O3 7.00% n.sub.e [589 nm, 20° C.]: 1.58 CPY-2-O2 8.00% Δε [1 kHz, 20° C.]: −3.0 CPY-3-O2 8.00% ε.sub.⊥ [1 kHz, 20° C.]: 6.4 PYP-2-3 3.00% K.sub.1 [pN, 20° C.]: 12.8 CC-3-V1 9.00% K.sub.3 [pN, 20° C.]: 14.4 CC-3-V 25.00% V.sub.0 [V, 20° C.]: 2.32 BCH-32 9.00% Σ 100.00%

Reference Example 7

(50) A liquid-crystal host mixture H-7 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(51) TABLE-US-00013 CCU-1-F 5.00% clearing point [° C.]: 85 CCU-2-F 8.00% Δn [589 nm, 20° C.]: 0.071 CCU-3-F 10.00% n.sub.e [589 nm, 20° C.]: 1.55 CCQU-3-F 11.00% Δε [1 kHz, 20° C.]: 4.2 CCQU-5-F 9.00% ε.sub.⊥ [1 kHz, 20° C.]: 3.2 CCZC-3-3 3.00% CCZC-4-5 3.00% CCZPC-3-5 3.00% CC-3-O1 11.00% CP-3-O1 12.00% CC-3-V1 6.00% CCP-V-1 10.00% CC-5-V 9.00% Σ 100.00%

Reference Example 8

(52) A liquid-crystal host mixture H-8 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(53) TABLE-US-00014 CC(CN)-4-7 14.00% clearing point [° C.]: 114.6 CC(CN)-5-5 14.00% Δn [589 nm, 20° C.]: 0.045 CC(CN)-3-3 6.00% n.sub.e [589 nm, 20° C.]: 1.52 CCZC-3-3 3.00% Δε [1 kHz, 20° C.]: −5.2 CCZC-3-5 3.00% ε.sub.⊥ [1 kHz, 20° C.]: 8.5 CCZC-4-3 3.00% CCZC-4-5 3.00% CC-3-O1 11.00% CC-5-O1 4.00% CC-5-O2 4.00% CC(CN)C-3-5 10.00% CC(CN)C-5-5 12.00% CC(CN)C-5-3 10.00% CCZPC-3-3 3.00% Σ 100.00%

Reference Example 9

(54) A liquid-crystal host mixture H-9 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(55) TABLE-US-00015 PGIGI-3-F 10.00% clearing point [° C.]: 105 CPG-2-F 6.00% Δn [589 nm, 20° C.]: 0.160 CPG-3-F 7.00% n.sub.e [589 nm, 20° C.]: 1.66 CPG-5-F 5.00% Δε [1 kHz, 20° C.]: 11.4 CPU-5-F 10.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.3 CPG-7-F 10.00% PGU-3-F 4.00% PGU-5-F 7.00% CCGU-3-F 8.00% CPP-3-2 4.00% CBC-33F 3.00% CBC-53F 3.00% CBC-55F 3.00% CPGU-3-OT 5.00% CP-5-N 15.00% Σ 100.00%

Reference Example 10

(56) A liquid-crystal host mixture H-10 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(57) TABLE-US-00016 CP-5-N 15.00% clearing point [° C.]: 92 CP-7-N 14.00% Δn [589 nm, 20° C.]: 0.163 CPG-2-F 6.00% n.sub.e [589 nm, 20° C.]: 1.67 CPG-3-F 6.00% CPG-5-F 5.00% PGU-2-F 9.00% PGU-3-F 9.00% PGU-5-F 9.00% CPP-3-2 7.00% CBC-33F 3.00% CBC-53F 3.00% CBC-55F 3.00% CBC-33 4.00% PGIGI-3-F 7.00% Σ 100.00%

Reference Example 11

(58) A liquid-crystal base mixture B-11 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

(59) TABLE-US-00017 CP-1V-N 10.00% clearing point [° C.]: 113 PZG-3-N 4.00% Δn [589 nm, 20° C.]: 0.297 PZG-4-N 13.00% n.sub.e [589 nm, 20° C.]: 1.82 PTP-1-O2 4.00% Δε [1 kHz, 20° C.]: 13.6 PTP-2-O1 5.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.5 PTP-3-O1 5.00% CPTP-3-O1 4.00% PPTUI-3-2 20.00% PPTUI-3-4 35.00% Σ 100.00%

(60) A mixture H-11 is prepared by mixing 98.41% of mixture B-11 with 1.59% of the compound of formula R-5011 as described in Table F above.

Examples 5 to 14

(61) Mixtures M-5 to M-14 are prepared analogous to mixture M-1 described in Example 1, wherein instead of host mixture H-1 respectively H-2 to H-11 are used as the host mixtures.

(62) The mixtures M-5 to M-14 are treated and analysed analogous to M-1 described in Example 1 above. The mixtures are suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.