LIQUID CRYSTALLINE MEDIUM

Abstract

The present invention relates to a liquid crystalline medium comprising dichroitic dyes made of benzothiadiazoles and related extended heterocyclic derivatives, the use of said medium for optical, electro-optical and electronic purposes, in particular in devices for regulating the passage of radiation energy from an outside space into an inside space, for example in windows. The invention further relates to devices containing the liquid crystalline medium according to the invention. Some new dichroitic dyes are disclosed.

Claims

1. Liquid crystalline medium comprising a dye component A) comprising one or more compounds of formula I, ##STR00543## and a liquid-crystalline component B) comprising one or more mesogenic compounds, where in formula I Ac independently of each other, denotes a group selected from ##STR00544## X independently is O, S, Se, NR.sup.2 or Te, Y.sup.1, Y.sup.2 independently are CR.sup.3 or N, R.sup.2 independently is H, alkyl having 1 to 25 C atoms or aryl, R.sup.3 is H, F, Cl, CN, alkyl having 1 to 25 C atoms, alkoxy having 1 to 25 C atoms or aryl, R.sup.11, R.sup.12 independently denote H, F, Cl, —CN, straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, 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—, —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, in addition, 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, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by —O—, —S—, —CO—, —CO—O—, —O—CO— o —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, 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 groups L, A.sup.21, A.sup.22 are each, independently of one another, defined like A.sup.11 or denote a cyclic alkyl group having 3 to 10 C atoms, in which one or more CH.sub.2 groups may be replaced by O in such a way that no two O atoms are adjacent, L on each occurrence, identically or differently, denotes OH, CH.sub.2OH, F, Cl, Br, I, —CN, —NO.sub.2, SF.sub.5, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.z).sub.2, —C(═O)R.sup.z, —N(R.sup.z).sub.2, optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, an aryl or heteroaryl group, which may be substituted by one or more F, Cl, C.sub.1-C.sub.6 alkyl or alkoxy, and alternatively two adjacent groups L together also denote a straight-chain or branched alkylene group having 2 to 10 C atoms, in which one, several or all H atoms may be replaced by F and in which one or more —CH.sub.2CH.sub.2— groups can be replaced by —CH═CH—, Z.sup.11, Z.sup.12 on each occurrence, identically or differently, denote a single bond, —CR.sup.x1═CR.sup.x2—, —C≡C— or —NR.sup.1—, R.sup.x1, R.sup.x2 independently of one another, denote H, F, Cl, CN or alkyl having 1-12 C atoms, R.sup.1 is H, F, alkyl having 1-12 C atoms or aryl, Z.sup.21, Z.sup.22 are on each occurrence, identically or differently, defined like Z.sup.11 or denote —O—, —S—, —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—, —CH═CH—COO or —OCO—CH═CH—, n1 denotes 1, 2, 3 or 4, R.sup.y1, R.sup.y2 each, independently of one another, denote H or alkyl having 1-12 C atoms, r, s independently of one another, denote 0, 1, 2 or 3, P denotes a single bond, —(CH.sub.2).sub.n—, —O(CH.sub.2).sub.mO—, —C≡C—, —NH—, —NR′—, —O(CO)O—, —O—, —S— or a group selected from the following partial groups: ##STR00545## wherein the ring elements Ar.sup.0, Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are as defined independently from the corresponding definitions, Ar.sup.0 is independently selected from the following formulae ##STR00546## Ar.sup.1 is independently selected from the following formulae ##STR00547## Ar.sup.4 is independently selected from the following formulae ##STR00548## Ar.sup.2, Ar.sup.3 are independently selected from the following formulae ##STR00549## W.sup.1 is S, O or Se, U.sup.1 is CR.sup.aR.sup.b, SiR.sup.aR.sup.b, GeR.sup.aR.sup.b, PR.sup.2 or NR.sup.2, wherein R.sup.a and Rb are independently defined as R.sup.4, R.sup.4-7 independently are H, F, Cl, CN, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR.sup.0—, —SiR.sup.0R.sup.00—, —CF.sub.2—, —CR.sup.x1═CR.sup.x2— or —C≡O— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, R.sup.0, R.sup.00 independently are H or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12, C atoms that is optionally fluorinated, Sp is a spacer group, preferably —O(CH.sub.2).sub.mO—, —(CH.sub.2).sub.n—, —NH— or —NR.sup.1—, m is 2 to 18, and and n is 1 to 18.

2. Liquid crystalline medium according to claim 1, characterised in that one or more compounds of formula I are selected from the compounds of formulae IA to IC ##STR00550## wherein the occurring groups and parameters have the meaning indicated for formula I in claim 1.

3. Liquid crystalline medium according to claim 1, characterised in that it comprises one or more compounds of formula IA selected from the group of compounds of the following subformulae: ##STR00551## where the groups occurring have the meanings: Z.sup.21, Z.sup.22 on each occurrence, identically or differently, preferably denote a single bond, —CR.sup.x1═CR.sup.x2—, —C≡C— or —C(O)—, particularly preferably a single bond, and P, A.sup.11, A.sup.12, A.sup.21, A.sup.22, Z.sup.11, Z.sup.12, R.sup.11, R.sup.12, R.sup.3, r and s are independently defined as in claim 1,

4. Liquid crystalline 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 a group L as defined in claim 1.

5. Liquid crystalline medium according to claim 1, which comprises one or more compounds of formula I wherein Z.sup.21 and Z.sup.22 denote a single bond.

6. Liquid crystalline medium according to claim 1, which comprises one or more compounds of formula I wherein R.sup.11 and R.sup.12 denote a branched alkyl group having 3 to 25 C atoms, in which one or more H atoms can be replaced by F, one or more CH.sub.2 groups can be replaced by O and/or NH and one or more CH groups can be replaced by N.

7. Liquid crystalline medium according to claim 1, which has negative dielectric anisotropy and comprises one or more compounds selected from the group of compounds of formulae CY, PY and AC ##STR00552## wherein ##STR00553## denotes ##STR00554## or ##STR00555## and ##STR00556## denote ##STR00557## or ##STR00558## denotes ##STR00559## R.sup.1, R.sup.2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, 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, preferably alkyl or alkoxy having 1 to 6 C atoms, R.sup.AC1, R.sup.AC2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, 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 0 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 to L.sup.4 each, independently of one another, denote F, Cl, CN, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, 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.

8. Liquid crystalline medium according to claim 1, which has positive dielectric anisotropy and comprises one or more compounds selected from the group of compounds of formulae II to VIII ##STR00560## wherein ##STR00561## and ##STR00562## each, independently of one another, denote ##STR00563## or ##STR00564## R.sup.20 each, identically or differently, denote a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, 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—, ##STR00565## —O—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, X.sup.20 each, identically or differently, denote 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 up to 6 C atoms, and Y.sup.20-24 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.

9. Liquid crystalline medium according to claim 1, which additionally comprises one or more compounds selected from the group of compounds of formulae DK and O ##STR00566## 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, in addition, 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, ##STR00567## denotes ##STR00568## or ##STR00569## denotes ##STR00570## or ##STR00571## denotes ##STR00572## or ##STR00573## and ##STR00574## denotes ##STR00575## or ##STR00576## 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.

10. Liquid crystalline medium according to claim 9, which comprises one or more compounds of formula O, selected from the group of compounds of the sub-formulae O3 to O5 ##STR00577## 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.

11. A method comprising incorporating liquid crystalline media according to claim 1 in: electro-optical displays, devices for regulating the passage of energy from an outside space into an inside space, electrical semiconductors, organic field-effect transistors (OFETs), printed circuits, radio frequency identification elements (RFIDs), organic light-emitting diodes (OLEDs), lighting elements, photovoltaic devices, optical sensors, effect pigments, decorative elements or dyes for colouring polymers.

12. Device for regulating the passage of energy from an outside space into an inside space, where the device contains a switching layer comprising a liquid crystalline medium according to claim 1.

13. Window containing a device according to claim 12.

14. Compounds of formula I ##STR00578## wherein the groups A.sup.11, A.sup.12, A.sup.21, A.sup.22, Z.sup.11, Z.sup.12, Z.sup.21, Z.sup.22, R.sup.11, R.sup.12, r and s each independently have the meaning indicated in claim 1, and wherein P denotes ##STR00579## or ##STR00580## or ##STR00581## wherein the variables are defined as in claim 1.

15. Compounds according to claim 14, characterised in that P is selected from the part formulae ##STR00582## wherein R.sup.2 is H, alkyl having 1 to 25 C atoms or aryl, each R.sup.4 is independently H, F, Cl, CN, or straight-chain, branched or cyclic alkyl with 1 to 30 atoms, in which one or more CH.sub.2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR.sup.0—, —SiR.sup.0R.sup.00—, —CF.sub.2—, —CR.sup.x1═CR.sup.x2— or —C≡O— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, R.sup.x1, R.sup.x2, independently of one another, denote H, F, Cl, CN or alkyl having 1-12 C atoms, and R.sup.0, R.sup.00 independently are H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

Description

EXAMPLES

[0354] The present invention is described in detail by the following, non-restrictive example.

[0355] All physical properties are determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status Nov. 1997, Merck KGaA, Germany, and apply for a temperature of 20° C. The value of Δn is determined at 589 nm, and the value of □□ is determined at 1 kHz, unless explicitly indicated otherwise in each case. n.sub.e and n.sub.o are in each case the refractive indices of the extraordinary and ordinary light beam under the conditions indicated above.

[0356] The degree of anisotropy R is determined from the value for the extinction coefficient E(p) (extinction coefficient of the mixture in the case of parallel alignment of the molecules to the polarisation direction of the light) and the value for the extinction coefficient of the mixture E(s) (extinction coefficient of the mixture in the case of perpendicular alignment of the molecules to the polarisation direction of the light), in each case at the wavelength of the maximum of the absorption band of the dye in question. If the dye has a plurality of absorption bands, the strongest absorption band is selected. The alignment of the molecules of the mixture is achieved by an alignment layer, as known to the person skilled in the art in the area of LC display technology. In order to eliminate influences by liquid-crystalline medium, other absorptions or reflections, each measurement is carried out against an identical mixture comprising no dye, and the value obtained is subtracted.

[0357] The measurement is carried out using linear-polarised light whose vibration direction is either parallel to the alignment direction (determination of E(p)) or perpendicular to the alignment direction (determination of E(s)). This can be achieved by a linear polariser, where the polariser is rotated with respect to the device in order to achieve the two different vibration directions. The measurement of E(p) and E(s) is thus carried out via the rotation of the vibration direction of the incident polarised light.

[0358] The degree of anisotropy R is calculated from the resultant values for E(s) and E(p) in accordance with the formula

R=[E(p)−E(s)]/[E(p)+2*E(s)],

as indicated, inter alia, in “Polarized Light in Optics and Spectroscopy”, D. S. Kliger et al., Academic Press, 1990. A detailed description of the method for the determination of the degree of anisotropy of liquid-crystalline media comprising a dichroic dye is also given in B. Bahadur, Liquid Crystals—Applications and Uses, Vol. 3, 1992, World Scientific Publishing, Section 11.4.2.

Example 1

[0359] ##STR00449##

Example 2

[0360] ##STR00450##

R=2-ethylhexyl

Example 3

[0361] ##STR00451##

R=2-ethylhexyl

[0362] The starting material is available according to C. Wetzel et al., Angew. Chem. Int. Ed. 2015, 54, 12334-12338.

Example 4

[0363] ##STR00452##

R=2-ethylhexyl

Example 5

[0364] ##STR00453##

R=2-ethylhexyl

Example 6

[0365] ##STR00454##

R=2-ethylhexyl

Example 7

[0366] ##STR00455##

R=2-ethylhexyl

Example 8

[0367] ##STR00456##

R=2-ethylhexyl

Example 9

[0368] ##STR00457##

R=2-ethylhexyl

Example 10

[0369] ##STR00458##

R=2-ethylhexyl

Example 11

[0370] ##STR00459##

R=2-ethylhexyl

Example 12

[0371] ##STR00460##

R=2-ethylhexyl

Example 13

[0372] ##STR00461##

Step 1:

[0373] ##STR00462##

[0374] 4-Bromo-7-chlorobenzo-1,2,5-thiadiazole (10.10 g, 40.03 mmol) and [4-(3-ethylheptyl)-2-fluorophenylboronic acid (10.91 g, 40.03 mol) are dissolved in THF (120 ml). After addition of water (24 ml), hydrazinium hydroxide (49 μl, 0.80 mmol, 80%), sodium metaborate tetrahydrate (8.28 g, 60.05 mmol) and bis(triphenylphosphine)palladium(II) chloride (15.2% of Pd) (562 mg, 0.80 mmol), the reaction mixture is stirred overnight at 70° C. Water and MTBE are added to the cooled reaction mixture. The combined organic phases are dried over sodium sulfate and filtered, and the solvent is removed. After purification by column chromatography (silica gel; chlorobutane), a yellow oil (12.1 g, 0.03 mol, GC: 95.9%) is isolated in a yield of 74%.

[0375] El-MS: m/z: 390.5.

[0376] The boronic acid is synthesised by procedures known from the literature. Bromochlorobenzothiadiazole is commercially available.

Step 2:

[0377] ##STR00463##

[0378] 4-Chloro-7-[4-(3-ethylheptyl)-2-fluorophenyl]benzo-1,2,5-thiadiazole (4.70 g, 0.012 mol) and 2-[9,9-dihexyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.38 g, 0.006 mol) are added to an aqueous NaHCO.sub.3 solution (0.97 g in 25 ml H.sub.2O). After addition of THF (55 ml) and bis(tri-t-butylphosphine)-palladium(O) (5.89 mg, 11.527 μmol), the reaction mixture is stirred overnight at 65° C. The organic phase is separated off and washed with water (2×200 ml). The further purification is carried out by column chromatography (silica gel; heptane/toluene: 1/1) and recrystallisation from heptane/chlorobutane. A slightly yellowish solid (1.70 g, 1.63 mmol, HPLC: 99.5%) is isolated in a yield of 28%.

[0379] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.09 (dd, J=7.8, 1.6 Hz, 2H), 8.03 (d, J=1.5 Hz, 2H), 7.97 (d, J=7.9 Hz, 2H), 7.91 (d, J=7.3 Hz, 2H), 7.85 (dd, J=7.3, 1.4 Hz, 2H), 7.72 (t, J=7.8 Hz, 2H), 7.20 (dd, J=7.8, 1.6 Hz, 2H), 7.15 (dd, J=11.3, 1.6 Hz, 2H), 2.77-2.59 (m, 4H), 2.19-2.11 (m, 4H), 1.67-1.71 (m, 4H), 1.47-1.29 (m, 18H), 1.13-1.21 (m, 12H), 0.92-0.98 (m, 16H), 0.81 ppm (t, J=6.8 Hz, 6H). DSC: TG 10 C 120 I.

Example 14

[0380] ##STR00464##

Step 1:

[0381] ##STR00465##

[0382] 2-Bromo-5-[4-(3-ethylheptyl)-2-fluorophenyl]thiophene (12.00 g, 31.18 mmol) and bis(pinacolato)diboron (10.50 g, 40.52 mmol) are dissolved in 1,4-dioxane (105 ml). After addition of PdCl2-dppf (686 mg, 0.94 mmol) and potassium acetate (9.20 g; 93.73 mmol), the reaction mixture is stirred overnight at 100° C. Water and MTBE are added to the cooled reaction mixture, and the aqueous phase is extracted a number of times with MTBE. After purification by column chromatography (silica gel, heptane/ethyl acetate: 1/1), a brown oil (9.4 g, GC: 82%) is isolated.

Step 2:

[0383] ##STR00466##

4-Bromo-7-chlorobenzo-1,2,5-thiadiazole (6.00 g, 23.78 mmol), 2-{5-[4-(3-ethylheptyl)-2-fluorophenyl]thien-2-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12.01 g, 23.78 mmol), bis(triphenylphosphine)palladium(II) chloride (15.2% of Pd) (334 mg, 0.48 mmol), hydrazinium hydroxide (49 μl, 0.48 mmol) and sodium metaborate tetrahydrate (4.92 g, 35.67 mmol) are dissolved in a solvent mixture of water (14 ml) and THF (70 ml) and stirred overnight at 70° C. Water and MTB are added to the cooled reaction mixture. The combined organic phases are dried over sodium sulfate and filtered, and the solvent is removed. After purification by column chromatography, an orange-red solid (9.40 g, 0.02 mol, HPLC: 99.4%) is isolated in a yield of 83%.

Step 3:

[0384] ##STR00467##

[0385] 4-Chloro-7-{5-[4-(3-ethylheptyl)-2-fluorophenyl]thien-2-yl}benzo-1,2,5-thiadiazole (1.00 g, 2.10 mmol), 2-[9,9-dihexyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.59 g, 1.01 mmol), THF (25 ml) and bis(tricyclohexylphosphine)-Pd(II) chloride (31 mg, 0.04 mmol) are added to a solution of sodium tetraborate (0.87 g, 6.31 mmol) in water (2 ml), and the mixture is stirred for 7 h at 65° C. After addition of toluene, the organic phase is separated off, and the solvent is removed. The further purification is carried out by column chromatography (silica gel; chlorobutane). A red resin (0.64 g, 0.53 mmol, HPLC: 99.0%) is isolated in a yield of 24%.

[0386] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.10 (d, J=3.7 Hz, 2H), 7.99-7.92 (m, 6H), 7.85 (d, J=7.8 Hz, 2H), 7.77 (d, J=7.3 Hz, 2H), 7.58 (t, J=8.0 Hz, 2H), 7.50 (d, J=3.7 Hz, 2H), 6.98-6.94 (m, 4H), 2.55 (dd, J=9.9, 6.4 Hz, 4H), 2.09-2.03 (m, 4H), 1.53 (dt, J=8.2, 5.5 Hz, 4H), 1.33-1.18 (m, 18H), 1.10-1.03 (m, 6H), 0.86-0.80 (m, 18H), 0.71 ppm (t, J=6.9 Hz, 6H). El-MS: m/z: 1206.7.

[0387] DSC: TG −2 I.

[0388] UV-Vis (THF): 228, 251, 336, 473 nm.

Example 15

[0389] ##STR00468##

[0390] Potassium acetate (6.14, 62.57 mmol), bis(tricyclohexylphosphine)-palladium(II) chloride (205 mg, 0.28 mmol), 1,4-dioxane (60 ml), 4-chloro-7-{5-[4-(3-ethylheptyl)-2-fluorophenyl]thien-2-yl}benzo-1,2,5-thiadiazole (13.16 g, 27.82 mmol) and triethylamine (46 μl, 0.33 mmol) are added to bis(pinacolato)diboron (4.37 g, 16.69 mmol), and the mixture is stirred overnight at 100° C. After addition of toluene and water, the organic phase is separated off, and the solvent is removed. The further purification is carried out by column chromatography (silica gel; toluene) and by recrystallisation from heptane. A red solid (0.58 g, 0.68 mmol, HPLC: 98.5%) is isolated in a yield of 5%.

[0391] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.47 (d, J=7.6 Hz, 2H), 8.19 (dd, J=3.9, 0.8 Hz, 2H), 8.08 (d, J=7.5 Hz, 2H), 7.65 (t, J=8.1 Hz, 2H), 7.57 (dd, J=4.0, 1.2 Hz, 2H), 7.07-6.99 (m, 4H), 2.67-2.58 (m, 4H), 1.65-1.56 (m, 4H), 1.43-1.19 (m, 18H), 0.93-0.88 ppm (m, 12H). DSC: C 213 I. UV-Vis (THF): 247, 329, 491 nm.

Example 16

[0392] ##STR00469##

Step 1:

[0393] ##STR00470##

[0394] Triphenylphosphine (86.60 g, 368.28 mmol) and 1,7-dibromoheptane (47.50 g, 184.11 mmol) are stirred overnight at 100° C. in DMF (600 ml). After the solvent is distilled off, the residue is stirred under reflux in MTBE (800 ml) and THF (200 ml). The cooled product (130.20 g, 81% yield, HPLC: 89.5%) is filtered off and dried in vacuo.

Step 2:

[0395] ##STR00471##

[0396] Potassium tert-butoxide (2.55 g, 22.27 mmol), dissolved in THF (20 ml), is added dropwise at 5° C. to a suspension of the phosphonium salt (9.00 g, 10.29 mmol) in THF (60 ml). After the mixture is stirred for 1 h at below 10° C., a solution of 4-bromo-3-fluorobenzaldehyde (4.10 g, 19.79 mmol) in THF (20 ml) is slowly added dropwise, and the mixture is stirred for 18 h at room temperature. A pH of 5 is established by addition of water and 2 N HCl. The phases are separated, and the aqueous phase is extracted with MTBE. The combined organic phases are washed with water, dried over sodium sulfate and filtered, and the solvent is removed. The residue is stirred in hot heptane and filtered, and the solvent is removed. After purification by column chromatography (silica gel, heptane/ethyl acetate: 95/5), a colourless oil (4.00 g, 0.01 mol, GC: 96%) was isolated as an E/Z isomer mixture in a yield of 79%.

Step 3:

[0397] ##STR00472##

[0398] The alkene (43.80 g, 83.84 mmol), conc. hydrochloric acid (0.17 ml, 1.76 mmol) and 5% Pt/C (5.00 g) are stirred in heptane (400 ml) under a hydrogen pressure atmosphere for 30 min at room temperature. The solvent is removed, and the residue obtained is recrystallised from ethanol. The product (38.80 g, 0.08 mol, GC: 93%) is obtained as a colourless solid in a yield of 91%.

[0399] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=7.41 (t, J=7.6 Hz, 2H), 6.93 (dd, J=9.7, 2.0 Hz, 2H), 6.83 (dd, J=8.1, 1.9 Hz, 2H), 2.55 (t, J=7.7 Hz, 4H), 1.62-1.52 (m, 4H), 1.30-1.25 ppm (m, 10H).

Step 4:

[0400] ##STR00473##

[0401] Bis(triphenylphosphine)palladium(II) chloride (15.2% of Pd) (0.70 g, 1.00 mmol), hydrazinium hydroxide (80%) (0.02 ml, 0.40 mmol), the dibromide (9.48 g, 0.02 mol) and THF (90 ml) are added to sodium metaborate tetrahydrate (5.50 g, 0.04 mol) in water (100 ml). A solution of thiophene-2-boronic acid (5.28 g, 0.04 mol) in THF (120 ml) is added to the mixture, which is then stirred overnight at 65° C. The cooled reaction mixture is extracted a number of times with MTBE. The combined organic phases are washed with water, dried over sodium sulfate and filtered, and the solvent is removed. After purification by column chromatography (silica gel, heptane), a crystalline solid (5.10 g, 0.01 mol) was isolated in a yield of 53%.

[0402] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=7.50 (t, J=8.0 Hz, 2H), 7.42 (d, J=3.7 Hz, 2H), 7.29 (dd, J=5.2, 1.1 Hz, 2H), 7.08-7.07 (m, 2H), 6.97-6.90 (m, 2H), 2.57 (t, J=7.8 Hz, 4H), 1.58 (m, 4H), 1.33-1.23 ppm (m, 10H). .sup.19F-NMR (CDCl.sub.3, 471 MHz): δ=−114.57-−114.62 ppm (m).

Step 5:

[0403] ##STR00474##

[0404] N-Bromosuccinimide is added in portions over the course of 30 min to a solution of compound 1 (21.00 g, 43.16 mmol) in chloroform (500 ml), and the mixture is stirred overnight with exclusion of light. After the solvent is removed, methanol (250 ml) is added, and the reaction mixture is warmed. The cooled residue is filtered off and recrystallised from heptane. The product is isolated as a colourless solid (23.7 g, 0.04 mol, HPLC: 97.6%) in a yield of 84%.

[0405] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=7.42 (t, J=8.1 Hz, 2H), 7.15 (dd, J=3.9, 0.8 Hz, 2H), 7.04 (dd, J=4.0, 0.8 Hz, 2H), 6.97-6.91 (m, 4H), 2.59 (t, J=7.7 Hz, 4H), 1.64-1.58 (m, 4H), 1.34-1.29 ppm (m, 10H). .sup.19F-NMR (CDCl.sub.3, 471 MHz): δ=−114.67 ppm (dd, J=11.9, 8.2 Hz).

Step 6:

[0406] ##STR00475##

[0407] Bis(pinacolato)diboron (134 mg, 0.52 mmol), potassium acetate (114 mg, 1.16 mmol) and Pd(dppf)Cl.sub.2 (9 mg, 0.01 mmol) are added to the monobromide (200 mg, 0.39 mmol) in 1,4-dioxane (5 ml), and the mixture is stirred overnight at 100° C. After addition of MTBE (10 ml) and water (20 ml) to the cooled solution, the organic phase is separated off, and the solvent is removed. The further purification is carried out by column chromatography (silica gel; toluene/ethyl acetate: 7/3). A wax-like solid (160 mg, 0.28 mmol, HPLC: 91.5%) is isolated in a yield of 67%.

[0408] El-MS: m/z: 564.3.

Step 7:

[0409] ##STR00476##

[0410] The dibromide (360 mg, 0.56 mmol) and the boronic ester (640 mg, 1.14 mmol) are dissolved in toluene (8 ml). After addition of 2 M NaCO.sub.3 solution (1.15 ml), tris(dibenzylideneacetone)dipalladium (5.20 mg, 0.01 mmol) and tris-(o)-tolylphosphine (7.10 mg, 0.02 mmol), the reaction mixture is stirred overnight at 110° C. After addition of hot toluene (50 ml), the mixture is cooled to RT. The solid formed is filtered off and washed with cold toluene, acetone and dichloromethane. A red solid (548 mg, 0.41 mmol, HPLC: 99.2%) is isolated in a yield of 71%.

[0411] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.10-8.08 (m, 4H), 7.86 (s, 4H), 7.62-7.59 (m, 4H), 7.50 (dd, J=4.0, 1.2 Hz, 4H), 7.02-6.95 (m, 8H), 2.64-2.59 (m, 8H), 1.41-1.23 (m, 34H), 0.93-0.87 ppm (m, 12H). .sup.19F-NMR (CDCl.sub.3, 376 MHz): δ=−113.95-−113.79 ppm (m). DSC: C 176 N (157) I. UV-Vis (THF): 258, 345, 493 nm.

Example 17

[0412] 1st step:

##STR00477##

[0413] 7,7-Bis(2-ethylhexyl)-2,5-bis(trimethylstannyl)-7H-3,4-dithia-7-silacyclopenta[a]pentalene (BTSi) (13.80 g, 0.02 mol) and 4,7-dibromo-1,2,5-thiadiazolo[3,4-c]pyridine (15.01 g, 0.05 mol) are dissolved in THF (35 ml). Tetrakis(triphenylphosphine)-palladium(O) (784 mg, 0.68 mmol) and N,N-dimethylformamide (35 ml) are added. The reaction mixture is stirred at 65° C. overnight. Water (15 ml) is added to the cooled mixture, and the solid formed is filtered off and washed a number of times with methanol. Purification by column chromatography (silica gel; heptane/chlorobutane: 1/1) enables a solid (9.00 g, 0.01 mol; HPLC: 98.7%) to be isolated in 62% yield.

[0414] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.73-8.75 (m; 2H), 8.63 (s; 2H), 1.51-1.54 (m; 2H), 1.06-1.38 (m; 20H), 0.78-0.82 ppm (m; 12H). .sup.13C-NMR (CDCl.sub.3, 176 MHz) δ 156.35, 153.86, 148.81, 147.95, 147.69, 147.67, 147.46, 146.02, 143.94, 139.96, 136.04, 136.02, 135.99, 107.62, 36.04, 35.78, 34.87, 29.47, 28.99, 28.96, 23.91, 23.00, 17.65, 14.19, 10.83 ppm.

[0415] El-MS: m/z: 846.1.

2nd step

##STR00478##

[0416] 2-(2-Ethylhexyl)thiophene (1.95 g, 0.01 mol) is dissolved in tetrahydrofuran (33 ml) and cooled to −70° C. n-BuLi (6.15 ml, 9.84 mmol; in hexane) is added dropwise, and the mixture is stirred at −70° C. for 1 h. Tributyltin chloride (2.78 ml, 9.84 mmol) is subsequently added, and the reaction mixture is warmed to RT. 5,5′-Bis{(4-(7-bromo-1,2,5-thiadiazolo[3,4-c]pyridinyl)}-3,3′-di-2-ethylhexylsilyl-2,2′-bithiophene (3.50 g, 4.69 mmol), tetrakis(triphenylphosphine)palladium(O) (216.58 mg, 0.19 mmol) and N,N-dimethylformamide (10 ml) are then added, and the mixture is stirred at 65° C. for 72 h. The solid formed is filtered off and purified by column chromatography. A dark-blue solid (620 mg, 0.57 mmol, HPLC: 99.0%) is be isolated.

[0417] The following derivatives are prepared by the same procedure:

Example 18

[0418] ##STR00479##

[0419] Blue solid, 25% yield, HPLC: 99.0%; .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.78 (s; 2H), 7.75 (m; 2H), 8.33 (s; 2H), 6.99 (s; 2H), 2.86 (d, J=6.8 Hz; 4H), 1.65-1.70 (m; 4H), 1.55-1.60 (m; 4H), 1.21-1.47 (m; 28H), 1.08-1.20 (m; 4H), 0.90-0.95 (m; 12H), 0.80-0.85 ppm (m; 12H).

[0420] UV-VIS (THF): 276, 312, 332, 630 nm.

Example 19

[0421] ##STR00480##

[0422] Blue solid, 15% yield, HPLC: 99.4%; .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.80 (s; 2H), 8.75 (m; 2H), 8.03 (d, J=3.8 Hz; 2H), 7.21 (d, J=3.8 Hz; 2H), 7.13 (d, J=3.5 Hz; 2H), 6.72 (d, J=3.5 Hz; 2H), 2.77 (d, J=6.7 Hz; 4H), 1.53-1.66 (m; 8H), 1.19-1.44 (m; 28H), 1.08-1.20 (m; 4H), 0.88-0.95 (m; 12H), 0.80-0.86 ppm (m; 12H).

[0423] UV-VIS (THF): 277, 366, 637 nm.

Example 20

[0424] 1st step:

##STR00481##

[0425] n-BuLi in hexane (1.6 M, 24.5 ml, 0.04 mol) is slowly added dropwise to a solution of 2-(2-ethylhexyl)thiophene (7.00 g, 35.65 mmol) at −70° C., and the reaction mixture is stirred at this temperature for 1 h. After addition of tributyltin chloride (11.08 ml, 0.04 mol), the mixture is stirred at −70° C. for a further 30 min and subsequently warmed to room temperature. After addition of 4,7-dibromobenzo-1,2,5-thiadiazole (10.48 g, 35.65 mmol), tetrakis(triphenylphosphine)palladium(O) (0.82 g, 0.7 mmol) and DMF (18 ml), the reaction mixture is warmed at 70° C. overnight. Water (30 ml) is added to the cooled solution, and the aqueous phase is extracted a number of times with toluene. After purification by column chromatography (silica gel; toluene/heptane: 1/1), a yellow oil (8.2 g, 19.91 mmol, HPLC: 99.4%) can be isolated in 56% yield.

2.sup.nd step:

##STR00482##

[0426] 4-Bromo-7-[5-(2-ethylhexyl)thien-2-yl]benzo-1,2,5-thiadiazole (3.02 g, 7.38 mmol), 7,7-bis(2-ethylhexyl)-2,5-bis(trimethylstannyl)-7H-3,4-dithia-7-silapenta[a]pentalene (2.00 g, 2.68 mmol) and tetrakis(triphenylphosphine)palladium(O) (113 mg, 0.10 mmol) are stirred in THF (15 ml) and DMF (5 ml) at 70° C. overnight. Water is added to the cooled reaction mixture, which is then extracted a number of times with MTBE. After purification by column chromatography (silica gel, toluene/heptane: 3/7), a violet oil (1.90 g, 1.75 mmol, HPLC: 99.0%) can be isolated in 71% yield.

[0427] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.17-8.19 (m; 2H), 7.97 (d, J=3.5 Hz; 4H), 7.84 (d, J=7.6 Hz; 2H), 7.80 (d, J=7.6 Hz; 2H), 6.87 (d, J=3.5 Hz; 2H), 2.83-2.85 (m; 4H), 1.64-1.69 (m; 2H), 1.18-1.43 (m; 34H), 1.03-1.14 (m; 4H), 0.90-0.94 (m; 12H), 0.80-0.86 ppm (m; 12H).

[0428] El-MS: m/z: 1074.8. DSC: TG −30 I. UV-VIS (THF): 316, 401, 474, 561 nm.

[0429] The following derivatives are prepared analogously:

Example 21

[0430] 1st step:

##STR00483##

[0431] Yellow solid, 47% yield, HPLC: 99.2%

2nd step:

##STR00484##

[0432] Blue crystals in 85% yield (HPLC: 99.5%); .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.38 (s, 2H), 8.19-8.21 (m; 2H), 7.80-7.84 (m; 4H), 6.97 (s; 2H) 1.51-1.54 (m, 2H), 2.85-2.86 (m; 4H), 1.64-1.69 (m; 2H), 1.54-1.58 (m; 2H), 1.20-1.45 (m; 32H), 1.05-1.15 (m; 4H), 0.90-0.94 (m; 12H), 0.81-0.85 ppm (m; 12H).

[0433] El-MS: m/z: 1186.4. DSC: TG −26 K 132 I. UV-VIS (THF): 336, 580 nm.

Example 22

[0434] 1st step:

##STR00485##

[0435] Red oil, 46% yield, HPLC: 99.2%

2nd step:

##STR00486##

[0436] Blue solid in 62% yield (HPLC: 99.6%); .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.19 (t, J=5.1 Hz; 2H), 8.03 (d, J=3.8 Hz; 2H), 7.79-7.87 (m; 4H), 7.19 (d, J=3.9 Hz; 2H), 7.11 (d, J=3.5 Hz; 2H), 6.68-6.73 (m; 2H), 2.76 (d, J=6.7 Hz; 4H), 1.55-1.63 (m; 4H), 1.26-1.45 (m; 24H), 1.20-1.24 (m; 8H), 1.05-1.15 (m; 4H), 0.90-0.94 (m; 12H), 0.81-0.85 (m; 12H).

[0437] El-MS: m/z: 1238.8. DSC: TG 8 K 117 I. UV-Vis (THF): 365, 592 nm.

Example 23

[0438] 1st step

##STR00487##

[0439] n-BuLi in hexane (1.6 M, 8.71 ml, 0.01 mol) is added dropwise to 2-(2-ethylhexyl)-4-hexyl-dithieno[3,2-b; 2′,3′-d]pyrrole (5.00 g, 13.27 mmol) in tetrahydrofuran (80 ml) at −70° C., and the mixture is stirred at this temperature for 45 min. After addition of tributyltin chloride (3.94 ml, 0.01 mol), the reaction mixture is stirred at this temperature for a further 30 min and subsequently warmed to room temperature. 4,7-Dibromobenzo-1,2,5-thiadiazole (11.72 g, 39.81 mmol), tetrakis(triphenylphosphine)palladium(O) (0.61 g, 0.5 mmol) and DMF (7 ml) are added, and the mixture is stirred at 70° C. overnight. Water and MTBE are added to the cooled reaction mixture. The aqueous phase is extracted a number of times with MTBE. The combined organic phases are washed with saturated NaCl solution and water. After purification by column chromatography (silica gel; heptane/toluene: 1/1) and recrystallisation from heptane and acetonitrile, a red solid (4.50 g, 7.61 mmol; HPLC: 99.5%) can be isolated in 57% yield.

[0440] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=8.28 (s; 1H), 7.80 (d, J=7.8 Hz; 1H), 7.66 (d, J=7.8 Hz; 1H), 6.70 (d, J=1.0 Hz; 1H), 4.23 (t, J=7.1 Hz; 2H), 2.82 (dd, J=6.9, 0.9 Hz; 2H), 1.87-1.93 (m; 2H), 1.65 (q, J=6.1 Hz; 1H), 1.25-1.47 (m, 14H), 0.82-0.96 ppm (m, 9H).

[0441] El-MS: m/z: 587.

Example 24

[0442] ##STR00488##

[0443] 2-(7-Bromobenzo-1,2,5-thiadiazol-4-yl)-6-(2-ethylhexyl)-4-hexyldithieno[3,2-b;2′,3′-d]pyrrole (2.55 g, 4.3 mmol), 7,7-bis(2-ethylhexyl)-2,5-bis(trimethylstannyl)-7H-3,4-dithia-7-silapenta[a]pentalene (1.40 g, 1.88 mmol) and tetrakis(triphenylphosphine)palladium(O) (80 mg, 0.07 mmol) are stirred in THF (15 ml) and DMF (4 ml) at 70° C. overnight. Water and toluene are added to the cooled reaction mixture. The aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with saturated NaCl solution. After purification by column chromatography (silica gel; heptane/toluene:3/2) and recrystallisation from heptane/toluene, a blue solid with a metallic lustre (1.90 g, 1.32 mmol; HPLC: 99.6%) can be isolated in 77% yield.

[0444] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.33 (s; 2H), 8.16-8.18 (m; 2H), 7.83-7.87 (m; 4H), 6.71 (s; 2H), 4.25 (t, J=7.1 Hz; 4H), 2.84 (d, J=6.9 Hz; 4H), 1.88-1.99 (m; 4H), 1.18-1.44 (m; 44H), 1.04-1.10 (m; 6H), 0.78-0.96 ppm (m; 32H).

[0445] El-MS: m/z: 1432.7. DSC: K 164 I. UV-VIS (THF): 295, 365, 633 nm.

Example 25

[0446] 1st step:

##STR00489##

[0447] n-BuLi in hexane (1.6 M, 10.35 ml, 0.02 mol) is added dropwise to 2-(2-ethylhexyl)thieno[3,2-b]thiophene (4.00 g, 15.77 mmol) in tetrahydrofuran (65 ml) at −70° C., and the mixture is stirred at this temperature for 45 min. After addition of tributyltin chloride (4.68 ml, 0.02 mol), the reaction mixture is stirred at this temperature for a further 30 min and subsequently warmed to room temperature. 4,7-Dibromo-1,2,5-thiadiazolo[3,4-c]pyridine (6.98 g, 23.65 mmol), tetrakis(triphenylphosphine)palladium(O) (0.36 g, 0.3 mmol) and DMF (8 ml) are added, and the mixture is stirred at 70° C. overnight. Water and toluene are added to the cooled reaction mixture. The aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with saturated NaCl solution and water. After purification by column chromatography (silica gel; heptane/toluene: 1/1) and recrystallisation from heptane and toluene, a red solid (4.40 g, 9.39 mmol; HPLC: 99.5%) can be isolated in 60% yield.

[0448] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=8.87 (s; 1H), 8.63 (s; 1H), 7.01 (s; 1H), 2.86 (d, J=6.8 Hz; 2H), 1.68 (m; 1H), 1.25-1.45 (m; 8H), 0.91 (m; 6H).

[0449] El-MS: m/z: 465.

2nd step:

##STR00490##

[0450] 7-Bromo-4-[5-(2-ethylhexyl)thieno[3,2-b]thien-2-yl-1,2,5-thiadiazolo[3,4-c]pyridine (3.27 g, 6.97 mmol), 7,7-bis(2-ethylhexyl)-2,5-bis(trimethylstannyl)-7H-3,4-dithia-7-silapenta[a]pentalene (2.70 g, 3.32 mmol) and tetrakis(triphenylphosphine)palladium(O) (153 mg, 0.13 mmol) are stirred in DMF (30 ml) at 100° C. overnight. Water and dichloromethane are added to the cooled reaction mixture.

[0451] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.82 (s; 2H), 8.77 (s; 2H), 8.18-8.20 (m; 2H), 7.02 (s; 2H), 2.87 (d, J=6.9 Hz; 4H), 1.67-1.72 (m; 2H), 1.28-1.46 (m; 26H), 1.20-1.26 (m; 8H), 1.08-1.16 (m; 4H), 0.90-0.95 (m; 12H), 0.80-0.88 ppm (m; 12H).

[0452] El-MS: m/z: 1188.7. DSC: K 230 I. UV-VIS (THF): 275, 302, 348, 603 nm.

Example 26

[0453] 1st step:

##STR00491##

[0454] N-BuLi in hexane (1.6 M, 19.6 ml, 0.03 mol) is slowly added dropwise to a solution of 2-(Dibutyl)-amino-thieno[3,2-b]thiophene (8.00 g, 0.03 mol) at −70° C., and the reaction mixture is stirred at this temperature for 1 h. After addition of tributyltin chloride (8.8 ml, 0.03 mol), the mixture is stirred at −70° C. for a further 30 min and subsequently warmed to room temperature. After addition of 4,7-dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (13.44 g, 0.04 mol), tetrakis(triphenylphosphine)palladium(O) (0.69 g, 0.7 mmol) and DMF (15 ml), the reaction mixture is warmed at 70° C. overnight. Water (30 ml) is added to the cooled solution, and the aqueous phase is extracted a number of times with toluene. After purification by column chromatography (silica gel; toluene/heptane: 7/3), a blue solid (9.0 g, 0.02 mol, HPLC: 99.0%) can be isolated in 62% yield.

2nd step:

##STR00492##

[0455] Bis-(pinacolato)-diborane (5.90 g, 22.77 mmol), Pd(dppf)Cl.sub.2 (0.33 g, 0.45 mmol), and K.sub.2CO.sub.3 (4.50 g, 45.85 mmol) were added to a solution of 2-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridin-4-yl)-N,N-dibutyl-thieno[3,2-b]thiophen-5-amine (7.30 g, 15.16 mmol) in 1,4-dioxane (110 ml) and stirred at 100° C. overnight. Water is added to the cooled reaction mixture, which is then extracted a number of times with toluene. The combined organic phases were dried over Na.sub.2SO.sub.4 and filtrated. After removal of the solvent, a red solid (6.10 g, 11.45 mmol) can be isolated in 76% yield.

[0456] .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ=8.82 (s, 1H), 8.81 (s, 1H), 6.03 (s, 1H), 3.32 (t, J=7.6 Hz, 4H), 1.72-1.64 (m, 4H), 1.42 (s, 12H), 1.42-1.36 (m, 4H), 0.98 (t, J=7.4 Hz, 6H).

[0457] El-MS: m/z: 528.0.

3rd step:

##STR00493##

[0458] 2,7-Dibromo-4,9-dihydro-4,4,9,9-tetra(2-ethylhexyl)-s-indaceno[1,2-b:5,6-b]-dithiophene (0.50 g, 0.57 mmol), N,N-dibutyl-2-[7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridin-4-yl]thieno[3,2-b]thiophen-5-amine (0.88 g, 1.67 mmol) and Pd.sub.2dba.sub.3 (11 mg, 0.01 mmol), SPhos (14 mg, 0.03 mmol), and Aliquat 336 (0.10 g, 0.25 mmol) are stirred in toluene (18 ml) and Na.sub.2CO.sub.3 solution (2M, 2.3 ml, 4.58 mmol) at 100° C. overnight. Water and toluene are added to the warm reaction mixture, which is then extracted a number of times with toluene. After purification by column chromatography (silica gel, toluene/heptane:1/1) and recrystallization (toluene/heptane), a green solid (0.70 g, 0.46 mmol, HPLC: 99.6%) can be isolated in 80% yield.

[0459] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.78 (t, J=4.3 Hz, 2H), 8.75 (s, 1H), 8.11-7.89 (m, 2H), 7.41 (s, 2H), 6.05 (s, 2H), 3.33 (t, J=7.7 Hz, 8H), 2.11-1.98 (m, 8H), 1.67-1.71 (m, 8H), 1.38-1.42 (m, 8H), 1.03-0.84 (m, 48H), 0.71-0.48 (m, 24H).

[0460] APCI-MS: m/z: 1515.7. DSC: TG 96 K 206 I. UV-VIS (THF): 279, 415, 687 nm.

[0461] 2,7-Dibromo-4,9-dihydro-4,4,9,9-tetra(2-ethylhexyl)-s-indaceno[1,2-b:5,6-b′]-dithiophene is available according McCulloch et al. J. Am. Chem. Soc. 2010, 132, 11437-11439.

[0462] The following derivatives are prepared analogously:

Example 27

[0463] 1st step:

##STR00494##

[0464] Red solid, 51% yield, HPLC: 99.8%

[0465] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.63 (s, 1H), 8.59 (d, J=3.9 Hz, 1H), 7.24 (d, J=3.9 Hz, 1H), 7.19 (d, J=3.6 Hz, 1H), 6.73 (d, J=3.5 Hz, 1H), 2.77 (d, J=6.8 Hz, 2H), 1.59-1.62 (m, 1H), 1.35-1.41 (m, 2H), 1.29-1.34 (m, 6H), 0.87-0.94 (m, 6H).

[0466] El-MS: m/z: 491.0.

2nd step:

##STR00495##

[0467] Red oil, 51% yield

[0468] El-MS: m/z: 539.4.

3rd step:

##STR00496##

[0469] 2,6-Dibromo-4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b:5,4-b′]dithiophene (1.70 g, 3.03 mmol), 4-[5-[5-(2-ethylhexyl)-2-thienyl]-2-thienyl]-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (4.10 g, 7.60 mmol) and Pd.sub.2dba.sub.3 (55 mg, 0.06 mmol), P(o-Tol).sub.3 (73 mg, 0.24 mmol), and Na.sub.2CO.sub.3 solution (2M, 12.1 ml, 24.2 mmol) at 100° C. overnight. Water and toluene are added to the cooled reaction mixture, which is then extracted a number of times with toluene. After purification by column chromatography (silica gel, toluene/heptane:1/1) and recrystallization (toluene/heptane), a blue solid (1.80 g, 1.47 mmol, HPLC: 99.9%) can be isolated in 48% yield.

[0470] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.83 (t, J=4.1 Hz, 2H), 8.60-8.57 (m, 2H), 8.10 (t, J=15.4 Hz, 2H), 7.26 (s, 2H), 7.20 (d, J=3.5 Hz, 2H), 6.73 (d, J=3.5 Hz, 2H), 2.78 (d, J=6.8 Hz, 4H), 2.10-2.04 (m, 4H), 1.64-1.60 (m, 2H), 1.42-1.27 (m, 16H), 1.10-0.95 (m, 16H), 0.94-0.89 (m, 12H), 0.84-0.80 (m, 2H), 0.67-0.64 (m, 12H).

[0471] APCI-MS: m/z: 1225.4. DSC: K 169 I. UV-VIS (THF): 279, 389, 639 nm.

Example 28

[0472] ##STR00497##

[0473] [5-(7-Bromo-[1,2,5]thiadiazolo[3,4-c]pyridin-4-yl)-thieno[3,2-b]thiophen-2-yl]-dibutyl-amine (4.03 g, 8.37 mmol), 7,7-bis(2-ethylhexyl)-2,5-bis(trimethylstannyl)-7H-3,4-dithia-7-silapenta[a]pentalene (3.05 g, 4.10 mmol) and tetrakis(triphenylphosphine)palladium(O) (173 mg, 0.15 mmol) are stirred in DMF (32 ml) at 100° C. overnight. Water is added to the cooled reaction mixture. The resulting solid is filtered off and further purified by column chromatography (silica gel, toluene/heptane: 1/1). The target compound is isolated as a green solid (1.69 g, 1.39 mmol) in 36% yield.

[0474] .sup.1H-NMR (CDCl.sub.3, 700 MHz): δ=8.71 (s; 4H), 8.08-8.12 (m; 2H), 8.18-8.20 (m; 2H), 6.04 (s; 2H), 3.32 (t, J=7.7 Hz; 8H), 1.67-1.71 (m; 8H), 1.38-1.42 (m; 8H), 1.28-1.36 (m; 8H), 1.20-1.26 (m; 8H), 1.08-1.14 (m; 4H), 0.99 (t, J=7.5 Hz; 12H), 0.80-0.88 ppm (m; 12H).

[0475] El-MS: m/z: 1218.8. DSC: TG 45 K 243 I. UV-VIS (THF): 401, 703 nm.

Example 29

[0476] 1st step:

##STR00498##

[0477] N-BuLi in hexane (1.6 M, 12.61 ml, 0.06 mol) is slowly added dropwise to a solution of 2-(Dibutyl)-amino-thieno[3,2-b]thiophene (5.00 g, 0.02 mol) in THF (130 ml) at −70° C., and the reaction mixture is stirred at this temperature for 1 h. After addition of tributyltin chloride (5.7 ml, 0.02 mol), the mixture is stirred at −70° C. for a further 30 min and subsequently warmed to room temperature. After addition of 4-bromo-7-chlorobenzo[1,2,5]thiadiazole (5.07 g, 0.02 mol), tetrakis(triphenylphosphine)palladium(O) (0.42 g) and DMF (19 ml), the reaction mixture is warmed at 70° C. overnight. Water (30 ml) is added to the cooled solution, and the aqueous phase is extracted a number of times with toluene. After purification by column chromatography (silica gel; toluene/heptane:1/1) and recrystallization from THF/acetonitrile, a blue solid (3.3 g, 0.01 mol, HPLC: 96.7%) can be isolated in 40% yield.

[0478] APCI-MS: m/z: 436.0.

2nd step:

##STR00499##

[0479] The distannane (0.39 g, 0.58 mmol) and dibutyl-[5-(7-chlorobenzo[1,2,5]thiadiazol-4-yl)-thieno[3,2-b]thiophen-2-yl]-amine (0.56 g, 1.28 mmol) were dissolved in toluene (10 ml) and placed under nitrogen. The reaction mixture was heated to 50° C. then Pd(OAc) (3 mg) and SPhos (10 mg) were added and the reaction heated to reflux for 24 hours. After cooling to room temperature, the product had precipitated out of solution. The toluene was reduced under vacuum then heptane was added and the mixture triturated then filtered. The dark purple solid was washed with heptane until no more purple filtrate came through (150 ml).

[0480] The crude material was applied to 5 g silica as a slurry in DCM. The pad was washed with heptane then 50% DCM/heptane, eluting some blue impurities until the clean product began to elute. Neat DCM then THF was used to elute the product. The solvent was removed to leave 0.5 g dark purple solid. The solid was triturated with methanol then collected by filtration and dried in a vacuum oven to leave dark purple solid (0.33 g, 0.29 mmol, HPLC: 99.9%) in 49% yield.

[0481] APCI-MS: m/z: 1146.27. DSC: K 249 I. UV-VIS (THF): 287, 401, 660 nm.

Example 30

[0482] ##STR00500##

[0483] [4-(2-ethylhexyl)-6-trimethylstannyl-dithieno[4,2-c:2′,4′-e]pyrrol-2-yl]-trimethyl-stannane (0.1 g, 0.11 mmol) and 2-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridin-4-yl)-N,N-dibutyl-thieno[3,2-b]thiophen-5-amine (0.13 g, 0.26 mmol) were dissolved in toluene (5 ml), placed under nitrogen and heated to 60° C. Pd(PPh.sub.3).sub.2Cl.sub.2 (3 mg) was added and the reaction was refluxed overnight. After purification by column chromatography (silica gel; DCM/ethyl acetate: 2:1), a blue solid (0.085 g, 0.08 mmol, HPLC: 98.9%) can be isolated in 70% yield.

[0484] El-MS: m/z: 1091.3. UV-VIS (THF): 281, 405, 723 nm.

[0485] The following compounds are made analogously:

##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508##

wherein
R denotes branched or linear alkyl with 1 to 12 C-atoms, preferably ethyl, n-propyl, iso-propyl, n-butyl, pentyl, hexyl or 3-ethylheptyl.

##STR00509## ##STR00510## ##STR00511## ##STR00512## ##STR00513## ##STR00514## ##STR00515## ##STR00516## ##STR00517## ##STR00518## ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## ##STR00531## ##STR00532## ##STR00533## ##STR00534## ##STR00535## ##STR00536##

wherein R is 2-ethylhexyl

Use Examples

[0486] The dyes prepared are investigated with respect to their physical properties in order to establish their suitability for use in devices for regulating energy transmission.

[0487] All percentages provided for the following compositions and in the general description are % by weight.

Preparation of Liquid-Crystalline Dye Mixtures

[0488] The following nematic LC host mixtures are composed as follows:

TABLE-US-00008 Mixture N-1: Composition Compound No. Abbreviation c [%] Physical properties 1 CPG-3-F 8 T(N,I) [° C.] = 114 2 CPG-5-F 8 Δn (20° C., 589.3 nm) = 0.130 3 CPU-5-F 14 Δε (20° C., 1 kHz) = 10.0 4 CPU-7-F 11 5 CP-5-N 18 6 CP-7-N 13 7 CCGU-3-F 7 8 CGPC-3-3 4 9 CGPC-5-3 4 10 CGPC-5-5 3 11 CCZPC-3-3 3 12 CCZPC-3-4 3 13 CCZPC-3-5 2 14 CC-3-O3 2 Σ 100

TABLE-US-00009 Mixture N-2: : Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-3-4- 14 T(N,I) [° C.] = 114.6 2 CC(CN)-5-5 14 Δn (20° C., 589.3 nm) = 0.045 3 CC(CN)-3-3 6 Δε (20° C., 1 kHz) = −5.2 4 CCZC-3-3 3 5 CCZC-3-5 3 6 CCZC-4-3 3 7 CCZC-4-5 3 8 CC-3-O1 11 9 CC-5-O1 4 10 CC-5-O2 4 11 CC(CN)C-3-5 10 12 CC(CN)C-5-5 12 13 CC(CN)C-5-3 10 14 CCZPC-3-3 3 Σ 100

TABLE-US-00010 Mixture N-3: Composition Compound No. Abbreviation c [%] Physical properties 1 CY-3-O2 12.0 T(N, I) [° C.] = 91.5 2 CY-5-O2 12.0 Δn (20° C., 589.3 nm) = 0.078 3 CCY-3-O2 13.0 Δϵ (20° C., 1 kHz) = −3.7 4 CCY-5-O2 13.0 LTS (−20° C.) [d] 27 5 CCY-3-1 8.0 6 CCZC-3-3 4.0 7 CCZC-3-5 3.0 8 CCZC-4-3 3.0 9 CC-3-4 6.0 10 CC-3-5 6.0 11 CC-3-O3 8.0 12 CC-5-O1 4.0 13 CC-5-O2 4.0 14 CP-3-O2 4.0 Σ 100

TABLE-US-00011 Mixture N-4: Composition Compound No. Abbreviation c [%] Physical properties 1 CY-3-O2 12.0 T(N, I) [° C.] = 79.5 2 CY-5-O2 13.0 Δn (20° C., 589.3 nm) = 0.100 3 CCY-3-O2 11.0 Δϵ (20° C., 1 kHz) = −3.1 4 CCY-5-O2 10.0 LTS (−20° C.) [d] >42 5 CCY-2-1 9.0 6 CPP-3-2 6.0 7 CPP-5-2 4.0 8 CGP-3-2 6.0 9 CC-3-4 6.0 10 CC-3-5 6.0 11 CP-3-O2 17.0 Σ 100

TABLE-US-00012 Mixture N-5: Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-4-7 20.0 T(N, I) [° C.] = 100.5 2 CC(CN)-5-5 21.0 Δn (20° C., 589.3 nm) = 0.044 3 CC-3-O1 11.0 Δϵ (20° C., 1 kHz) = −4.8 4 CC-5-O1 5.0 LTS (−20° C.) [d] >42 5 CC-5-O2 5.0 6 CCZC-3-3 4.0 7 CCZC-3-5 4.0 8 CCZC-4-3 4.0 9 CCZC-4-5 4.0 10 CC(CN)C-5-5 22.0 Σ 100

TABLE-US-00013 Mixture N-6: Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-3-3 10.0 T(N, I) [° C.] = 106.0 2 CC(CN)-4-7 10.0 Δn (20° C., 589.3 nm) = 0.118 3 CC(CN)-5-7 10.0 Δϵ (20° C., 1 kHz) = −6.0 4 CY-3-O2 5.0 LTS (−20° C.) [d] >73 5 PPC(CN)-5-3 13.0 6 CCY-3-O2 5.0 7 CCY-3-O3 5.0 8 CCY-4-O2 6.0 9 CPY-2-O2 9.0 10 CPY-3-O2 8.0 11 PYP-2-3 7.0 12 PYP-2-4 6.0 13 CGPC-3-3 2.0 14 CGPC-5-3 2.0 15 CGPC-5-5 2.0 Σ 100

TABLE-US-00014 Mixture N-7: : Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-3-3 8.0 T(N, I) [° C.] = 113.5 2 CC(CN)-4-7 8.0 Δn (20° C., 589.3 nm) = 0.127 3 CC(CN)-5-5 9.0 Δϵ (20° C., 1 kHz) = −6.0 4 CY-3-O2 5.0 LTS (−20° C.) [d] >100 5 PPC(CN)-5-3 12.0 6 CCY-3-O2 5.0 7 CCY-3-O3 5.0 8 CCY-4-O2 6.0 9 CPY-2-O2 9.0 10 CPY-3-O2 8.0 11 PYP-2-3 7.0 12 PYP-2-4 6.0 13 CGPC-3-3 2.0 14 CGPC-5-3 2.0 15 CGPC-5-5 2.0 16 CPP-3-2 3.0 17 CPP-5-2 3.0 Σ 100

TABLE-US-00015 Mixture N-8: Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-3-3 13.0 T(N, I) [° C.] = 107.5 2 CC(CN)-4-7 15.0 Δn (20° C., 589.3 nm) = 0.103 3 CC(CN)-5-5 12.0 Δϵ (20° C., 1 kHz) = −4.9 4 PPC(CN)-5-3 10.0 LTS (−20° C.) [d] >83 5 CPY-2-O2 5.0 6 CPY-3-O2 5.0 7 CCY-4-O2 5.0 8 PYP-2-3 10.0 9 CP-3-O1 8.0 10 CGPC-3-3 4.0 11 CGPC-5-3 3.0 12 CGPC-5-5 3.0 13 CCZPC-3-3 3.0 14 CCZPC-3-4 2.0 15 CCZPC-3-5 2.0 Σ 100

TABLE-US-00016 Mixture N-9: : Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-4-7 10.0 T(N, I) [° C.] = 111.5 2 CC(CN)-5-5 10.0 Δn (20° C., 589.3 nm) = 0.124 3 CY-3-O2 6.0 Δϵ (20° C., 1 kHz) = −4.7 4 CP-3-O1 10.0 LTS (−20° C.) [d] >73 5 PPC(CN)-5-3 10.0 6 CPY-2-O2 7.0 7 CPY-3-O2 7.0 8 CCY-3-O2 6.0 9 CCY-5-O2 7.0 10 PYP-2-3 10.0 11 CGP-3-2 6.0 12 CGPC-3-3 3.0 13 CGPC-5-3 3.0 14 CGPC-5-5 2.0 15 CCZPC-3-3 3.0 Σ 100

TABLE-US-00017 Mixture N-10: Composition Compound No. Abbreviation c [%] Physical properties 1 CC(CN)-3-3 8.0 T(N, I) [° C.] = 107.5 2 CC(CN)-4-7 10.0 Δn (20° C., 589.3 nm) = 0.129 3 CC(CN)-5-5 10.0 Δϵ (20° C., 1 kHz) = −5.5 4 CY-3-O2 10.0 LTS (−20° C.) [d] >73 5 CPP(F,CN)-5-O2 10.0 6 CPY-2-O2 6.0 7 CPY-3-O2 9.0 8 CCY-4-O2 5.0 9 PYP-2-3 10.0 10 PYP-2-4 10.0 11 CGPC-3-3 3.0 12 CGPC-5-3 3.0 13 CGPC-5-5 3.0 14 CCZPC-3-3 3.0 Σ 100

TABLE-US-00018 Mixture N-11 : Composition Compound No. Abbreviation c [%] Physical properties 1 CY-3-O2 9.0 T(N, I) [° C.] = 110.5 2 CY-3-O4 9.0 Δn (20° C., 589.3 nm) = 0.132 3 CY-5-O2 12.0 Δϵ (20° C., 1 kHz) = −4.9 4 CY-5-O4 8.0 LTS (−20° C.) [d] >76 5 CCY-3-O2 5.0 6 CCY-3-O3 5.0 7 CCY-4-O2 5.0 8 CPY-2-O2 7.0 9 CPY-3-O2 6.0 10 PYP-2-3 12.0 11 CCP-V-1 6.0 12 CCZPC-3-3 3.0 13 CCZPC-3-4 3.0 14 CGPC-3-3 5.0 15 CGPC-5-3 5.0 Σ 100

TABLE-US-00019 Mixture N-12: Composition Compound No. Abbreviation c [%] Physical properties 1 CC-3-V 41.5 T(N ,I) [° C.] = 74.0 2 CCY-3-O1 5.0 Δn (20° C., 589.3 nm) = 0.101 3 CCY-3-O2 11.0 Δϵ (20° C., 1 kHz) = −3.5 4 CCY-4-O2 6.0 LTS (−20° C.) [d] 13 5 CPY-2-O2 5.0 6 CPY-3-O2 11.0 7 CY-3-O2 3.5 8 PY-3-O2 12.0 9 B-3-O2 5.0 Σ 100

TABLE-US-00020 Mixture N-13: : Composition Compound No. Abbreviation c [%] Physical properties 1 CC-3-V 40.5 T(N, I) [° C.] = 74.0 2 CCY-3-O1 5.0 Δn (20° C., 589.3 nm) = 0.101 3 CCY-3-O2 11.0 Δϵ (20° C., 1 kHz) = −3.6 4 CCY-4-O2 6.0 LTS (−20° C.) [d] 15 5 CPY-2-O2 5.5 6 CPY-3-O2 11.0 7 CY-3-O2 5.0 8 PY-3-O2 12.0 9 B-3-O2 4.0 Σ 100

TABLE-US-00021 Mixture N-14: Composition Compound No. Abbreviation c [%] Physical properties 1 CY-3-O2 12.5 T(N, I) [° C.] = 110.5 2 CCY-3-O1 9.0 Δn (20° C., 589.3 nm) = 0.132 3 CCY-3-O2 11.0 Δϵ (20° C., 1 kHz) = −4.9 4 CCY-4-O2 7.0 LTS (−20° C.) [d] >76 5 CPY-3-O2 3.0 6 CC-3-V 31.0 7 B-2O-O5 4.0 8 PY-V2-O2 5.5 9 CPY-V-O2 6.0 10 CPY-V-O4 5.0 11 CCY-V-O2 6.0 Σ 100

TABLE-US-00022 Mixture N-15: : Composition Compound No. Abbreviation c [%] Physical properties 1 CCGU-3-F 6.0 T(N, I) [° C.] = 109.5 2 CCQU-3-F 12.0 Δn (20° C., 589.3 nm) = 0.0986 3 CCQU-5-F 10.0 Δϵ (20° C., 1 kHz) = +9.0 4 CCU-3-F 10.0 LTS (−20° C.) [d] >42 5 CGPC-3-3 6.0 6 CP-3-O1 10.0 7 CCZU-3-F 15.0 8 CCZU-5-F 1.5 9 PGUQU-3-F 2.5 10 CPGU-3-OT 4.0 11 CPG-3-F 4.0 12 CPP-3-2 5.0 13 CC-3-4 4.0 14 CC-3-5 5.0 15 CC-3-O1 5.0 Σ 100

TABLE-US-00023 Mixture N-16: Composition Compound No. Abbreviation c [%] Physical properties 1 CPU-3-F 11.0 T(N,I ) [° C.] = 124.0 2 CPU-5-F 11.0 Δn (20° C., 589.3 nm) = 0.1695 3 CGU-2-F 7.0 Δϵ (20° C., 1 kHz) = +12.4 4 CGU-3-F 8.0 LTS (−20° C.) [d] n/a 5 PGU-2-F 9.0 6 PGU-3-F 9.0 7 PGU-5-F 7.0 8 CCGU-3-F 8.0 9 CCP-V-1 6.0 10 CPPC-3-3 3.0 11 CGPC-3-3 5.0 12 CGPC-5-3 5.0 13 CGPC-5-5 5.0 14 PGIGI-3-F 6.0 Σ 100

TABLE-US-00024 Mixture N-17: Composition Compound No. Abbreviation c [%] Physical properties 1 CC-3-O1 8.0 T(N, I) [° C.] = 108.5 2 CCP-3-1 4.0 Δn (20° C., 589.3 nm) = 0.1082 3 CCP-3-3 7.0 Δϵ (20° C., 1 kHz) = +13.4 4 CP-3-O1 8.0 LTS (−20° C.) [d] >42 5 CCP-3-OT 9.0 6 CCP-5-OT 5.0 7 CPU-3-F 10.0 8 CCQU-3-F 20.0 9 CCGU-3-F 2.5 10 PUQU-3-F 3.0 11 APUQU-2-F 5.0 12 APUQU-3-F 8.0 13 PGUQU-3-F 5.0 14 CPGU-3-OT 3.5 15 CPGP-4-3 2.0 Σ 100

TABLE-US-00025 Mixture N-18: Composition Compound No. Abbreviation c [%] Physical properties  1 CC-3-V1 10.0 T(N, I) [° C.] = 114.3  2 PGUQU-3-F 4.0 Δn (20° C., 589.3 nm) =  0.0861  3 CCGU-3-F 5.5 Δε (20° C., 1 kHz) = +11.2  4 CCG-3-OT 9.0 LTS (−20° C.) [d] >28  5 CPU-3-F 11.0  6 CPU-5-F 4.0  7 CCQU-3-F 10.0  8 CCQU-5-F 7.5  9 CCZU-2-F 4.0 10 CCZU-3-F 12.0 11 CCZU-5-F 4.0 12 CCEG-3-F 12.0 13 CCEG-5-F 7.0 Σ 100

TABLE-US-00026 Mixture N-19: Composition Compound No. Abbreviation c [%] Physical properties  1 CPG-3-F 5.0 T(N, I) [° C.] =    114.5  2 CPG-5-F 5.0 Δn (20° C., 589.3 nm) =     0.1342  3 CPU-3-F 15.0 Δε (20° C., 1 kHz) =    11.3  4 CPU-5-F 15.0 LTS (−20° C.) [d] >1049  5 CP-3-N 16.0  6 CP-5-N 16.0  7 CCGU-3-F 7.0  8 CGPC-3-3 4.0  9 CGPC-5-3 4.0 10 CGPC-5-5 4.0 11 CCZPC-3-3 3.0 12 CCZPC-3-4 3.0 13 CCZPC-3-5 3.0 Σ 100

TABLE-US-00027 Mixture N-20: Composition Compound No. Abbreviation c [%] Physical properties  1 PZG-2-N 0.936 T(N, I) [° C.] = 108.5  2 PZG-3-N 0.936 Δn (20° C., 589.3 nm) =  0.1082  3 PZG-4-N 2.184 Δε (20° C., 1 kHz) = +13.4  4 PZG-5-N 2.184 LTS (−20° C.) [d] n/a  5 CP-3-O1 7.488  6 CC-3-4 3.120  7 CPP-3-2 2.496  8 CCZGI-3-3 2.496  9 CCZGI-3-5 2.496 10 CCZPC-3-3 1.248 11 CCZPC-3-4 1.248 12 CCZPC-3-5 0.936 13 CPZG-3-N 1.248 14 CGPC-5-3 1.248 15 CPPC-5-3 0.936 16 CPU-3-F 34.400 17 CPU-5-F 34.400 Σ 100

TABLE-US-00028 Mixture N-21: Composition Compound No. Abbreviation c [%] Physical properties 1 CP-5-3 20.0 T(N, I) [° C.] = n/a 2 CC-3-5 10.0 Δn (20° C., 589.3 nm) = 0.0730 3 CCU-2-F 12.0 Δε (20° C., 1 kHz) = n/a 4 CCU-3-F 10.0 LTS (−20° C.) [d] n/a 5 CCU-5-F 8.0 6 CCEG-3-F 10.0 7 CCEG-5-F 10.0 8 CCG-3-OT 10.0 9 CCG-5-OT 10.0 Σ 100

Device Examples

[0489] For the following device examples, the nematic host mixtures N-1 and N-2 are used and mixtures with the following dyes are prepared:

##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541##

Single-Dye Mixture Examples for Evaluation

[0490]

TABLE-US-00029 TABLE 1 For each dye the absorption maximum λ.sub.max, the isotropic extinction coefficient and the degree of anisotropy R in the base mixture N-1 are provided. The concentration is about 0.1 mass %. isotropic extinction Mixture coefficient [1/(mass- example Dye λ.sub.max [nm] %*cm)] R M-1 Ref-1 459 375 0.78 M-2 Ref-2 505 395 0.71 M-3 Ref-3: 585 465 0.73 M-4 Ref-4: 670 275 0.68 M-5 Ref-5: 779 345 0.66 M-6 D-1 486 432 0.76 M-7 D-2 426 371 0.68 M-8 D-3 530 454 0.74 M-9 D-4 507 454 0.75 M-10 D-5 487 550 0.78 M-11 D-6 585 465 0.70 M-12 D-7 590 560 0.78 M-13 D-8 605 511 0.76 M-14 D-9 617 520 0.78 M-15 D-10 633 505 0.70 M-16 D-11 656 540 0.74 M-17 D-12 590 560 0.73 M-18 D-13 668 555 0.71

[0491] The mixtures M-6 to M-18 are very well suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows. The mixtures have a suitable combination of high extinction, high degree of anisotropy (R) and good long term stability.

[0492] Multi-Dye Mixtures for Applications

[0493] The values shown in Table 1 as well as the corresponding values below are measured according to norm EN410.

[0494] The following mixtures are provided which are designed to have a neutral grey switching state:

Mixture Example E-1

[0495] The following mixture is prepared and investigated.

TABLE-US-00030 Component concentration c [%] D-1 0.166 D-2 0.261 D-3 0.084 D-9 0.288 N-1 Rest to 100

Mixture Example E-2

[0496] The following mixture is prepared and investigated.

TABLE-US-00031 Component concentration c [%] D-1 0.220 D-2 0.902 D-3 0.221 D-9 1.130 N-2 Rest to 100

Mixture Example E-3

[0497] The following mixture is prepared and investigated.

TABLE-US-00032 Component concentration c [%] D-2 0.168 D-3 0.118 D-5 0.151 D-11 0.294 N-1 Rest to 100

Mixture Example E-4

[0498] The following mixture is prepared and investigated.

TABLE-US-00033 Component concentration c [%] D-2 0.884 D-3 0.328 D-5 0.428 D-11 1.046 N-2 Rest to 100

Mixture Example E-5

[0499] The following mixture is prepared and investigated.

TABLE-US-00034 Component concentration c [%] D-1 0.347 D-9 0.253 D-11 0.079 N-1 Rest to 100

Mixture Example E-6

[0500] The following mixture is prepared and investigated.

TABLE-US-00035 Component concentration c [%] D-2 0.65 D-7 0.43 N-1 Rest to 100

Mixture Example E-7

[0501] The following mixture is prepared and investigated.

TABLE-US-00036 Component concentration c [%] D-2 1.379 D-7 1.45  N-2 Rest to 100

Comparative Example C-1

[0502] The following comparative mixture C-1 is prepared and investigated.

TABLE-US-00037 Component concentration c [%] Ref-1 0.930 Ref-2 0.367 Ref-3 0.987 Ref-4 0.039 N-2 Rest to 100

[0503] The mixtures provided above are filled into test cells: [0504] a) Double cell: Two parallel TN cells (twisted nematic, 90°) with 25 μm cell gap. [0505] b) Single cell: VA cells (vertical alignment; rubbing direction 240°) with 15 μm cell gap.

TABLE-US-00038 TABLE 2 Total amounts of dye for a transmission τ.sub.v in the bright state of the device of 59-62%, and the difference between on-state and off-state (Δτ.sub.v). Total amount τ.sub.v τ.sub.v Δτ.sub.v Mixture Type dyes bright state dark state difference E-1 double cell 0.799% 62.7% 10.0% 52.7% E-2 single cell 2.473% 61.7% 18.0% 43.7% E-3 double cell 0.731% 61.6% 13.5% 48.1% E-4 single cell 2.686% 61.4% 21.3% 40.1% E-5 double cell 0.679% 61.6% 10.9% 51.3% E-6 Double cell  1.08% 61.7%  9.1% 52.6% E-7 single cell 2.829% 61.7% 16.8% 44.9% C-1 single cell 3.001% 61.7% 17.7%   44%

[0506] The mixtures E-1 to E-7 have a balanced grey or colorless appearance in one of the switching states.

[0507] The mixtures are very well suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows. The mixtures according to the invention have a suitably high difference between of the extinction in the on-state and off-state for the transmittance of white light, while at the same time the concentrations of dye are low.

[0508] A single cell with the conventional mixture C-1 requires a higher total amount of dyes (3.0%) in order to achieve a comparable extinction.

Stability in Sunlight Conditions

[0509] The relative extinction of samples is tested under daylight conditions (Suntest CPS by MTS Atlas; cut-off filter GG400 by Schott) at 20° C. base temperature. The surface temperature is 43° C.

[0510] The test is continued until the relative extinction drops to 80%.

[0511] As a standard 300 ppm of a stabilizer is added to the mixtures, which is of the following formula:

##STR00542##

[0512] The lifetime of the mixtures according to the invention exceeds 4 weeks.

TABLE-US-00039 TABLE 3 Minimum lifetimes under suntest. Compound Stability D-6 74 weeks D-7 66 weeks D-8 76 weeks D-9 68 weeks D-10 70 weeks D-11 58 weeks D-12 68 weeks D-13 62 weeks