Device for regulating the passage of energy

Abstract

The present application relates to novel compounds and to devices which contain these compounds. The application also relates to a device for regulating the passage of energy from an outside space into an inside space, to a window containing the said device, and to uses of the said devices and compounds.

Claims

1. Compound of the formula (I): ##STR00043## where: X is equal to S or Se; Z.sup.1 is, independently of one another, a single bond, CR.sup.3CR.sup.3 or CC; or two, three, four or five groups combined with one another, selected from the groups CR.sup.3CR.sup.3 and CC; Z.sup.2 is, independently of one another, a single bond, O, S, C(R.sup.3).sub.2, CR.sup.3CR.sup.3 or CC; or two, three, four or five groups combined with one another, selected from the groups O, S, C(R.sup.3).sub.2, CR.sup.3CR.sup.3 and CC; Ar.sup.1 is, independently of one another, an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4; R.sup.1 is, independently of one another, H, D, F, CN, N(R.sup.5).sub.2, or an alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, which may be substituted by one or more radicals R.sup.5, where one or more CH.sub.2 groups in the alkyl, alkoxy or thioalkoxy groups may be replaced by R.sup.5CCR.sup.5, CC, CO, CS, C(O)O, OC(O), Si(R.sup.5).sub.2, NR.sup.5, O or S; R.sup.3, R.sup.4 are, independently of one another, H, D, F, Cl, CN, or an alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms, which may be substituted by one or more radicals R.sup.5, where one or more CH.sub.2 groups in the alkyl, alkoxy or thioalkoxy groups may be replaced by R.sup.5CCR.sup.5, CC, CO, CS, C(O)O, OC(O), Si(R.sup.5).sub.2, NR.sup.5, O or S; R.sup.5 is, independently of one another, H, D, F, Cl, CN, N(R.sup.6).sub.2, an alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.6 and where one or more CH.sub.2 groups in the above-mentioned groups may be replaced by R.sup.6CCR.sup.6, CC, CO, CS, C(O)O, O(CO), Si(R.sup.6).sub.2, NR.sup.6, O or S, or an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.6; R.sup.6 is, independently of one another, H, F or an aliphatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by F, or an aryl or heteroaryl group having 5 to 20 C atoms, in which one or more H atoms may be replaced by F; and i is, independently of one another, equal to 0, 1, 2, 3, 4 or 5.

2. Compound according to claim 1, characterised in that X is equal to S and/or in that Z.sup.1 is a single bond.

3. Compound according to claim 1, characterised in that Z.sup.2 stands, independently of one another, for a single bond, C(R.sup.3).sub.2C(R.sup.3).sub.2, CR.sup.3CR.sup.3, CC, OC(R.sup.3).sub.2 or C(R.sup.3).sub.2O.

4. Compound according to claim 1, characterised in that Z.sup.1 and Z.sup.2 stand for a single bond.

5. Compound according to claim 1, characterised in that Ar.sup.1 represents, independently of one another, an aryl group having 6 to 15 C atoms or a heteroaryl group having 5 to 15 C atoms, which may be substituted by one or more radicals R.sup.4.

6. Compound according to claim 1, characterised in that Ar.sup.1 is selected on each occurrence from benzene, fluorene, naphthalene, pyridine, pyrimidine, pyrazine, triazine, thiophene, thiophene with condensed-on 1,4-dioxane ring, benzothiophene, dibenzothiophene, benzodithiophene, cyclopentadithiophene, thienothiophene, indenothiophene, dithienopyrrole, silolodithiophene, selenophene, benzoselenophene, dibenzoselenophene, furan, benzofuran, dibenzofuran and quinoline, each of which is optionally substituted by radicals R.sup.4.

7. Compound according to claim 1, characterised in that at least one Ar.sup.1 is selected from a sulfur-containing heteroaryl group, which may be substituted by one or more radicals R.sup.4.

8. Compound according to claim 1, characterised in that R.sup.1 is selected, independently of one another, from H, F, or a straight-chain alkyl or alkoxy group having 3 to 20 C atoms, which may be substituted by one or more radicals R.sup.5, or a branched alkyl or alkoxy group having 3 to 20 C atoms, which may be substituted by one or more radicals R.sup.5, or a cyclic alkyl group having 6 C atoms, which may be substituted by one or more radicals R.sup.5, where one or more CH.sub.2 groups in the alkyl and alkoxy groups may be replaced by O, S or R.sup.5CCR.sup.5, or a siloxanyl group having 1 to 6 Si atoms, which may be substituted by one or more radicals R.sup.5.

9. Compound according to claim 1, characterised in that R.sup.1 is, independently of one another, a branched alkyl group having 4 to 15 C atoms.

10. Compound according to claim 1, characterised in that the index i is equal to 1 or 2.

11. Compound according to claim 1, characterised in that the degree of anisotropy R of the compound of the formula (I) is greater than 0.4.

12. A device for regulating the passage of energy from an outside space into an inside space which is a window or switchable window where the device contains a switching layer, where the switching layer comprises one or more compounds of the formula (I).

13. A device according to claim 12, characterised in that, besides the compound of the formula (I), a liquid-crystalline medium comprising one or more different compounds is present in the switching layer.

14. A device according to claim 12, characterised in that it is electrically switchable.

15. A device according to claim 12, characterised in that it is connected to a solar cell or another device for conversion of light and/or heat energy into electrical energy.

Description

FIGURE

Brief Description of Drawing

(1) FIG. 1 shows a UV-VIS spectrum of the compound V2 prepared in accordance with Working Example 2, with absorption peaks at 227, 332, 404, 471 and 487 nanometers. The absorption (OD) is shown as a function of the wavelength (nm).

WORKING EXAMPLES

(2) The examples show the preparation of dichroic fluorescent dyes based on 2-(2,5,7-trithia-1,3-diaza-s-indacen-6-ylidene)malononitrile (TDIM). They are intended to illustrate the present invention and should not be interpreted as restrictive.

Example 1a: Preparation of Compound V1

(3) Compound 3 is prepared from compound 1 in accordance with the synthetic route shown in Scheme 4:

(4) ##STR00039##

Preparation of Compound 2

(5) A mixture of 1 (Schroeder et al., 2012; Li et al., 2014) (1.50 g, 3.04 mmol), (2-ethylbutoxy)benzeneboronic acid (1.62 g, 7.3 mmol), tris(dibenzylideneacetone)dipalladium(0) (32 mg, 0.035 mmol), tris(o-tolyl)phosphine (42 mg, 0.138 mmol), toluene (52 ml) and 2 M aqueous Na.sub.2CO.sub.3 solution (30 ml) is heated under reflux under an argon atmosphere for 18 h. The mixture is subjected to conventional aqueous work-up. The crude product obtained from the organic extracts is filtered through a silica-gel frit (toluene/n-heptane 1:1) and subsequently crystallised three times from toluene. Yield of compound 2: (1.3 g, 62%) as red crystals, HPLC purity 99.5%.

Preparation of Compound 3

(6) A mixture of 2 (1.00 g, 1.45 mmol) and dimercaptomethylenemalononitrile disodium salt (Hatchard, 1964) (350 mg, 1.88 mmol) and NMP (50 ml) is stirred at 90 C. under an argon atmosphere for 18 h. The mixture is poured into water (300 ml) and allowed to crystallise out for 18 h. The solid which has precipitated out is filtered off with suction and filtered through a silica-gel frit (toluene/n-heptane 1:1). The residue is recrystallised from hot toluene/n-heptane 5:3. Yield of compound 3: (370 mg, 32%) as red crystals, HPLC purity 99.7%. HR-MS (C.sub.42H.sub.39O.sub.2N.sub.4S.sub.5): 791.16664.

Example 1b: Preparation of Compound V2

(7) ##STR00040##

(8) Compound V2 is prepared by an analogous route to Example 1a, by coupling a 2-ethylheptyloxy-substituted phenylboronic acid instead of the 2-ethylbutoxyphenylboronic acid indicated in Example 1a.

Example 2: Preparation of Compound V3

(9) Compound 5 is prepared from compound 1 in accordance with the synthetic route shown in Scheme 5:

(10) ##STR00041##

Preparation of Compound 4

(11) A mixture of compound 1 (Schroeder et al., 2012; Li et al., 2014) (8.00 g, 16.19 mmol), 4-(2-ethylheptyl)-2-fluorobenzeneboronic acid (8.80 g, 33.06 mmol), tris(dibenzylideneacetone)dipalladium(0) (171 mg, 0.187 mmol), tris(o-tolyl)phosphine (224 mg, 0.736 mmol), toluene (280 ml) and 2 M aqueous Na.sub.2CO.sub.3 solution (65 ml) is heated under reflux under an argon atmosphere for 18 h. The mixture is subjected to conventional aqueous work-up. The crude product obtained from the organic extracts is filtered through a silica-gel frit (toluene/n-heptane 1:4) and subsequently crystallised twice from n-heptane/toluene 1:1. Yield of compound 4: (8.2 g, 66%) as red crystals, HPLC purity 99.3%.

Preparation of Compound 5

(12) A mixture of 4 (1.94 g, 2.5 mmol) and dimercaptomethylenemalononitrile disodium salt (Hatchard, 1964) (930 mg, 5.00 mmol) and NMP (25 ml) is stirred at RT under an argon atmosphere for 24 h. The mixture is poured into water (200 ml) and allowed to crystallise out for 1 h. The solid which has precipitated out is recrystallised from toluene (30 ml) and subsequently filtered through a silica-gel frit (toluene). The residue is recrystallised again from toluene (20 ml). Yield of compound 5: (1.1 g, 50%) as red crystals, HPLC purity 99.4%. HR-MS (C.sub.48H.sub.49N.sub.4F.sub.2S.sub.5): 879.25234. FIG. 1 shows a UV-VIS spectrum of compound 5 (1.3 mg in 100 ml of tetrahydrofuran) with absorption peaks at 227, 332, 404, 471 and 487 nanometers.

Example 3: Measurement of the UV-VIS Absorption Spectra of Compounds V1 and V3

(13) Absorption spectra of the two compounds mentioned above in THF (compound V1, 1.3 mg in 100 ml of tetrahydrofuran, see FIG. 1), or in dichloromethane (compound V3) are recorded.

(14) The spectra have the following peaks:

(15) TABLE-US-00002 Compound Absorption peaks at [nm] V1 330; 345; 400; 520 V3 227; 332; 404; 471; 487

Example 4: Use of Liquid-Crystalline Media Comprising the Dyes According to the Invention in Devices for Regulating the Passage of Light

(16) In order to produce the devices, the liquid-crystal mixture comprising one of the dyes according to the invention is introduced into the interspace of the following layer arrangement (single cell): substrate layer ITO layer polyimide alignment layer interspace held open using spacers polyimide alignment layer ITO layer substrate layer;

(17) or introduced into the interspaces of the following layer arrangement (double cell): substrate layer ITO layer polyimide alignment layer interspace held open using spacers polyimide alignment layer ITO layer substrate layer substrate layer ITO layer polyimide alignment layer interspace held open using spacers polyimide alignment layer ITO layer substrate layer,

(18) i.e. comprising two single cells arranged one behind the other, where the alignment layers of the second single cell have a rubbing direction rotated by 90 relative to the alignment layers of the first single cell (crossed single cells).

(19) The liquid-crystal layer in this arrangement is aligned in a planar manner with antiparallel pretilt angle. This alignment is achieved by two polyimide layers rubbed antiparallel to one another. The thickness of the liquid-crystalline layer is defined by spacers and is usually 25 m.

(20) Values for the degree of light transmission .sub.v for both the dark and bright switching states of the device are determined and are shown below. The bright switching state is achieved by application of a voltage, while the dark switching state is present without voltage. Furthermore, the colour location of the device (in CIE coordinates) in the dark and bright states is determined.

(21) The measurement is carried out with the device comprising the liquid-crystalline medium with dyes in the measurement beam and a device of the same construction correspondingly without the dyes in the reference beam. Reflection and absorption losses of the cell are thereby eliminated.

(22) The value .sub.v and the CIE coordinates (x,y) are defined as follows:

(23) .sub.v=degree of light transmission, determined in accordance with DIN EN410

(24) The colour location (for white, grey, black) of the basic standard illuminant D65 here is at x=0.3127 and y=0.3290 (Manfred Richter, Einfhrung in die Farbmetrik [Introduction to Colorimetry], second edition 1991, ISBN 3-11-008209-8). The colour locations (x,y) indicated all relate to the standard illuminant D65 and the 2 standard observer in accordance with CIE 1931.

(25) The following mixture serves as host mixture (Ml):

(26) TABLE-US-00003 Composition of host mixture M1 Clearing point 114.5 C. Delta-n 0.1342 n.sub.e 1.6293 n.sub.o 1.4951 Compound % by weight Composition CPG-3-F CPG-5-F 5 CPU-3-F 5 CPU-5-F 15 CP-3-N 15 CP-5-N 16 CCGU-3-F 16 CGPC-3-3 7 CGPC-5-3 4 CGPC-5-5 4 CCZPC-3-3 4 CCZPC-3-4 3 CCZPC-3-5 3

(27) These are the structures of the other compounds used below:

(28) ##STR00042##

Example 4a

(29) The following liquid-crystalline mixture is used:

(30) TABLE-US-00004 Constituent Proportion [%] M1 99.029 D1 0.188 V1 0.118 D2 0.061 D3 0.604

(31) Measurement values obtained for the device (double cell, 25 m in each case): dark state: x=0.312; y=0.329; .sub.v=15% bright state: x=0.334; y=0.358; .sub.v=70.6%

Example 4b

(32) TABLE-US-00005 Constituent Proportion [%] M1 98.035 D1 0.221 V1 0.243 D2 0.158 D3 0.680 D4 0.663

(33) Measurement values obtained for the device (single cell, 25 m): dark state: x=0.313; y=0.329; .sub.v=38% bright state: x=0.322; y=0.344; .sub.v=72%

Example 4c

(34) TABLE-US-00006 Constituent Proportion [%] M1 99.029 D1 0.153 V1 0.20 V2 0.255 D2 0.199 D3 1.111 D4 1.156

(35) Measurement values obtained for the device (single cell, 25 m): dark state: x=0.313; y=0.329; .sub.v=30% bright state: x=0.322; y=0.3.sup.46; .sub.v=60%

(36) The examples show that the device can be switched from a dark state having significantly lower light transmission to a bright state having significantly increased light transmission by application of a voltage.