Dihydronaphthalene derivatives

Abstract

The present invention relates to dihydronaphthalene derivatives of formula D specified in claim 1; to a liquid crystalline medium comprising a compound of formula D; and to high-frequency components containing these media, in particular microwave components for high-frequency devices such as devices for phase shifting microwaves, tunable filters, tunable metamaterial structures, and electron beam controlled antennas such as phased array antennas.

Description

[0001] The present invention relates to dihydronaphthalene derivatives; liquid crystal media containing the same; and high-frequency components containing these media, in particular microwave components for high-frequency devices, such as devices for microwave phase shifting, tunable filters, tunable metamaterial structures, and electron beam steering antennas (e.g., phased array antennas), as well as devices containing the components. The present invention also relates to optical components containing the liquid crystal media, which are operable in the infrared (IR) region of the electromagnetic spectrum. The present invention also relates to the use of the LC media in the IR region and to devices including the optical components.

[0002] Liquid crystal media have been used for many years in electro-optical displays (liquid crystal displays: LCD) for displaying information. However, more recently, liquid crystal media have also been proposed for use in components for microwave technology, for example in DE 10 2004 029 429 A and JP 2005-120208 (A).

[0003] The corresponding properties of the known liquid crystal mixture E7 (Merck KGaA, Germany) are described in “Direct Simulation of Material Permittivities using an Eigen-Susceptibility Formulation of the Vector Variational Approach” by A. Gaebler, F. Goelden, S. Müller, A. Penirschke and R. Jakoby, 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467.

[0004] DE 10 2004 029 429 A describes the use of liquid-crystalline media in microwave technology, in particular in phase shifters. Liquid-crystalline media and their properties in the corresponding frequency range are discussed therein, and liquid-crystalline media based on mixtures of predominantly aromatic nitriles and isothiocyanates are shown.

[0005] However, compositions that can be used in microwave applications still have several disadvantages. There is a need to improve the general physical properties, shelf life, and stability of these media during operation in the device. Given the many different parameters that must be considered and improved in order to develop liquid-crystalline media for microwave applications, it would be desirable to have a wider range of possible mixture components for developing such liquid-crystalline media.

[0006] It was an object of the present invention to provide compounds for liquid-crystalline media which have improved properties in connection with applications in the microwave range of the electromagnetic spectrum.

[0007] To solve this problem, there are provided compounds of the formula D defined below and liquid-crystalline media comprising these compounds.

[0008] The present invention relates to a compound of formula D

[0009]

[0010] in

[0011] R D represents H, a straight-chain alkyl radical having 1 to 12 C atoms or a branched-chain alkyl radical having 2 to 12 C atoms, or a straight-chain alkenyl radical having 2 to 12 C atoms, or a branched-chain alkenyl radical having 3 to 12 C atoms, or a straight-chain alkynyl radical having 2 to 12 C atoms or a branched-chain alkynyl radical having 4 to 12 C atoms, wherein one or more CH2- groups may be replaced by and one or more non-adjacent CH2- groups may be replaced by O or alternatively represent a group R P ,

[0012] R P Indicates halogen, CN, NCS, R F -、R F -O- or R F -S-, where

[0013] R F represents a fluorinated alkyl group having 1 to 9 C atoms,

[0014] Z D1 , Z D2 , Z D3 and Z D4 Identically or differently represent -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -N=N-, -C=NN=C-, -CH=N-, -N=CH-, -C≡C-, -C≡CC≡C- or a single bond, wherein

[0015] Z D1 represents -O-, -S-, -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -C2F4-, -CH2CF2-, -CF2CH2-, -CH=CH-CH2O-, -CH=CH-CO-O-, -OCH2-CH=CH- or -O-CO-CH=CH-,

[0016] X D Indicates -C≡C-CN, -NCS or -C≡C-NCS,

[0017] and Identically or differently represent a group selected from the following group:

[0018] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, in which one or two CH groups may be replaced by N and in which one or more H atoms may be replaced by L,

[0019] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4′-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, in which one or two CH groups may be replaced by N, one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-, and in which one or more H atoms may be replaced by L,

[0020] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L,

[0021] express wherein one or more H atoms are optionally replaced by L,

[0022] L, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or in each case optionally fluorinated, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having 1 to 12 C atoms,

[0023] t1, t2, t3 and t4 are the same or different and are 0, 1 or 2, preferably 0 or 1,

[0024] Wherein t1+t2+t3+t4 is 1, 2 or 3, preferably 1 or 2.

[0025] According to another aspect of the present invention, a liquid-crystalline medium is provided which comprises one or more compounds of formula D.

[0026] Preferred embodiments of the invention are subject matter of the independent claims or can be taken from the description.

[0027] Surprisingly, it has been found that by using compounds of the formula D in liquid-crystalline media, liquid-crystalline media can be achieved which have excellent stability and at the same time high dielectric anisotropy, suitably fast switching times, a suitable nematic phase range, high tunability and low dielectric losses (in the microwave range of the electromagnetic spectrum).

[0028] In particular, the medium according to the invention comprising the compound according to the invention is characterized by an improved quality factor η due to a higher tunability τ and lower dielectric losses.

[0029] The medium according to the invention is further characterized by a high brightness temperature, a broad nematic phase range and excellent low temperature stability (LTS). Thus, devices containing this medium can be operated under extreme temperature conditions.

[0030] The medium is further characterized by a high dielectric anisotropy value and a low rotational viscosity. Consequently, the threshold voltage (i.e., the minimum voltage at which the device can switch) is very low. To achieve devices with improved switching characteristics and high energy efficiency, low operating voltages and low threshold voltages are necessary. The low rotational viscosity enables fast switching of the device according to the present invention.

[0031] These properties overall make the medium particularly suitable for components and devices for high-frequency technology and applications in the microwave range, in particular devices for microwave phase shifting, tunable filters, tunable metamaterial structures and electronic beam steering antennas (e.g. phased array antennas).

[0032] According to another aspect of the invention there is therefore provided a component and an apparatus comprising said component, both operable in the microwave region of the electromagnetic spectrum.Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuits and adaptive filters.

[0033] The media according to the invention are likewise suitable for use in the infrared region of the electromagnetic spectrum.

[0034] Therefore, the present invention further relates to the use of the medium defined above for phase modulation of said infrared light in the infrared region of the electromagnetic spectrum, preferably in the A-band and / or B-band and / or C-band.

[0035] According to another aspect of the present invention, there is provided an optical assembly comprising a liquid crystal medium according to the present invention sandwiched between a pair of substrates.

[0036] The present invention further relates to devices comprising the optical assembly according to the present invention. Preferred devices are infrared imagers, wavelength selective switches, LCoS-SLMs, LIDAR systems, wavelength division multiplexing (WDM) systems, reconfigurable optical add / drop multiplexers (ROADMs), and non-mechanical beam steering, such as the controllable electrically transient optical refraction (SEEOR) prisms disclosed in the article P. McManamon, 2006, "Agile Nonmechanical Beam Steering," Opt. Photon. News 17(3):24-29.

[0037] According to another aspect of the present invention, there is provided a method for spatially modulating infrared light, the method comprising:

[0038] i) providing an optical component comprising a first substrate and a second substrate facing each other, each having a surface, the first substrate comprising at least one first electrode, the second substrate comprising at least one second electrode, the component further comprising a liquid crystal layer sandwiched between the first substrate and the second substrate, wherein the liquid crystal comprises one or more compounds selected from the compounds of formula D indicated above;

[0039] ii) receiving incident infrared light at a surface of the optical component;

[0040] iii) applying a predetermined voltage to each of the individual electrodes formed on the first substrate and the second substrate to modulate the refractive index of the liquid crystal layer.

[0041] According to another aspect of the present invention, there is provided a method for manufacturing an optical phase modulator, comprising at least the following steps:

[0042] a) providing a first substrate having a first electrode, optionally with a two-dimensional array of individually electrically actuatable cartridges;

[0043] b) depositing the liquid crystal medium according to claim 1 on a first substrate;

[0044] and

[0045] c) Mounting a second substrate having a second electrode onto the liquid crystal material.

[0046] The optical component according to the invention is characterized by excellent operational stability when exposed to the environment, due to the high brightness temperature, wide nematic phase range and excellent low-temperature stability (LTS) of the liquid-crystalline medium used therein. Consequently, the component and the device containing it can be operated under extreme temperature conditions.

[0047] The medium used for the assembly according to the application is characterized by a high dielectric anisotropy value and a low rotational viscosity. Thus, the threshold voltage, i.e. the minimum voltage at which the device can switch, is very low. In order to have an improved switching behavior and high energy efficiency of the device, a low operating voltage and a low threshold voltage are required. The low rotational viscosity enables fast switching of the assembly and the device according to the application.

[0048] Herein, "high frequency technology" means an application of electromagnetic radiation with a frequency in the range of 1 MHz to 1 THz, preferably 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, and in particular preferably about 5 GHz to 150 GHz.

[0049] As used herein, the infrared region of the electromagnetic spectrum refers to the spectral region of electromagnetic radiation having a wavelength in the range of 0.75 pm to 1000 pm.

[0050] As used herein, Infrared A (IR-A) refers to the spectral region of electromagnetic radiation having a wavelength in the range of 0.75 pm to 1.4 pm.

[0051] As used herein, Infrared B (IR-B) refers to the spectral region of electromagnetic radiation having a wavelength in the range of 1.4 pm to 3 pm.

[0052] As used herein, Infrared C (IR-C) refers to the spectral region of electromagnetic radiation having a wavelength in the range of 3 pm to 1000 pm.

[0053] Preferably, the optical assembly according to the application operates at a wavelength in the range of 750 nm to 2500 nm, in particular 1530 nm to 1565 nm.

[0054] Very preferred light sources for the use according to the application are IR lasers emitting light at a wavelength of 1,55 pm or IR lasers emitting light at a wavelength of 905 nm.

[0055] As used herein, halogen is F, CI, Br or I, preferably F or CI, in particular preferably F.

[0056] Herein, alkyl is linear or branched or cyclic and has 1 to 15 C atoms, preferably is linear and has 1, 2, 3, 4, 5, 6 or 7 C atoms, thus preferably is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl, unless indicated otherwise.

[0057] Herein, branched alkyl is preferably iso-propyl, sec-butyl, iso-butyl, iso-pentyl, 2-methylbutyl, 2-methylhexyl or 2-ethylhexyl.

[0058] As used herein, cyclic alkyl refers to straight-chain or branched alkyl or alkenyl groups having up to 12 C atoms, preferably alkyl groups having 1 to 7 C atoms, in which the CH group is replaced by a carbocyclic ring having 3 to 5 C atoms, very preferably selected from cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl and cyclopentenylalkyl.

[0059] Herein, alkoxy is straight-chain or branched and contains 1 to 15 C atoms. It is preferably straight-chain and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is therefore preferably methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy or n-heptoxy.

[0060] In this article, alkenyl is preferably an alkenyl with 2 to 15 C atoms, which is straight or branched and contains at least one C-C double bond. It is preferably straight and has 2 to 7 C atoms. Therefore, it is preferably vinyl, prop-1- or -2-alkenyl, but-1-, -2- or -3-alkenyl, penta-1-, -2-, -3- or -4-alkenyl, hex-1-, -2-, -3-, -4- or -5-alkenyl, hept-1-, -2-, -3-, -4-, -5- or -6-alkenyl. If two C atoms of the C-C double bond are substituted, alkenyl can be in the form of E and / or Z isomers (trans / cis). Generally, corresponding E isomers are preferred. In alkenyl, particularly preferred prop-2-alkenyl, but-2- and -3-alkenyl and penta-3- and -4-alkenyl.

[0061] In this context, alkynyl is understood to mean an alkynyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one C—C triple bond. 1-Propanyl and 2-propynyl as well as 1-, 2-butynyl and 3-butynyl are preferred.

[0062] If R F represents a halogenated alkyl, alkoxy, alkenyl or alkenyloxy radical, which may be branched or unbranched. Preferably, it is unbranched, monofluorinated, polyfluorinated or perfluorinated, preferably perfluorinated and has 1, 2, 3, 4, 5, 6 or 7 C atoms, in the case of alkenyl, 2, 3, 4, 5, 6 or 7 C atoms.

[0063] R P Preferably, it represents CN, NCS, Cl, F, -(CH2) n -CH=CF2、-(CH2) n -CH=CHF, -(CH2) n -CH=Cl2、-C n F 2n+1 、-(CF2) n -CF2H, -(CH2) n -CF3, -(CH2)n -CHF2, -(CH2) n CH2F, -CH=CF2, -O(CH2) n -CH=CF2、-O(CH2) n CHCl2, -OC n F 2n+1 、-O(CF2) n -CF2H, -O(CH2) n CF3, -O(CH2) n -CHF2, -O(CF) n CH2F, -OCF=CF2, -SC n F 2n+1 、-S(CF) n -CF3, wherein n is an integer from 0 to 7.

[0064] The compounds of the general formula D are prepared by methods known per se, as described in the literature (for example in standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart) and under reaction conditions known and suitable for the reaction. Variants known per se but not mentioned in greater detail herein can be used here.

[0065] If desired, the starting substances can also be formed in situ by not isolating them from the reaction mixture, but by reacting them immediately further to form the compounds of the general formula D.

[0066] Preferred synthetic routes to the compounds according to the invention are illustrated in the following reaction schemes, in which the radicals and parameters occurring have the meanings given for formula D. They are further illustrated with the aid of working examples and can be adapted to the particular desired compounds of the general formula D by selecting suitable starting materials.

[0067] Fluorinated dihydronaphthalenes are described in JP 2003-146919 A ​​and JP 2003-183196 A .

[0068] Preferred starting materials are suitably substituted dihydronaphthalenes (1) carrying two different reactive groups X 1 and X 2 .

[0069]

[0070] Since the group X 1 and X 2The reactivity of the group X is different. By selecting appropriate reaction conditions, the group X can be selectively 1 and X 2 One of the reactions, then with the help of X 1 and X 2 Another group in is derived. Suitable group X 1 and X 2 is a leaving group selected from, but not limited to, Cl, Br, I, methanesulfonate (MsO), methylphenylsulfonate (TsO), trifluoromethanesulfonate (TfO), perfluorononylsulfonate (NsO), etc. This principle is described in the paper E. Shirakawa et al., cobalt-catalyzed cross-coupling of alkynyl Grignard reagents with alkenyl triflates, Chem. Commun., 2007, 4513-4515. Wherein, a compound of formula 1 is shown, wherein X 1 represents TfO and X 2 Represents Br(1a).

[0071]

[0072] Compound 1a can be prepared from 6-bromo-2-tetralone; 6-chloro-2-tetralone and 6-iodo-2-tetralone are also known from the literature and can be reacted in an analogous manner.

[0073] According to one aspect of the present invention, there is provided a method for producing a compound of formula D, wherein the compound of formula (1) is reacted in two steps by two different transition metal catalyzed cross-coupling reactions (Scheme 1). D2 Preferred compounds of the formula D having a triple bond are obtained, for example, from compound 1a by Sonogashira coupling.

[0074] Option 1:

[0075]

[0076] Compound 1 can also be reacted in other cross-coupling reactions, such as the Suzuki reaction described in WO2017133521A1, to give intermediate 5; in this embodiment, Z of formula D D2 is a single bond (Scheme 2).

[0077] Option 2

[0078]

[0079] Analogously to known protocols, the vinyl linking group is introduced via Heck (Scheme 3, M = H) or Stille coupling (Scheme 3, M = Bu3Sn-), as described in Scott, William J.; Pena, Michael R.; Sward, Katerina; Stoessel, Steven J.; Stille, JK, Journal of Organic Chemistry 50(13), 2302-8 and Roth, Gregory P.; et al., Tetrahedron Letters (1995), 36(13), 2191-4.

[0080] Option 3

[0081]

[0082] Another suitable starting material for the synthesis of compounds according to the present invention is 6-hydroxy-2-tetralone, wherein the hydroxyl group can first be protected with a suitable phenol protecting group (PG), such as methoxymethyl (MOM), as described in the paper Katherine M. Byrd, Caitlin N. Kent and Brian SJ Blagg, ChemMedChem 2017, 12, 2022-2029, and then the hydroxyl group can be further reacted in an analogous manner to the bromo-derivative 1a (Scheme 4) via the triflate 8.

[0083] Option 4

[0084]

[0085] Compound 11 was transferred to intermediate 12 by the same method described above (Scheme 5), where G is a group that can be transferred to X D Groups in:

[0086] Option 5

[0087]

[0088] For example, a preferred precursor for synthesizing the compound of formula D is an amino derivative of formula N1

[0089]

[0090] The compound of formula N1 is reacted with a thiocarbonic acid derivative Reaction, wherein X and Y are leaving groups, or reaction with CS2 to obtain a compound of formula D.

[0091] Preferred reagents for the process according to the invention for converting the compound of formula N1 into the compound of formula D are carbon disulfide, thiophosgene, thiocarbonyldiimidazole, di-2-pyridylthiocarbonate, bis(dimethylthiocarbamoyl)disulfide, dimethylaminothiocarbonyl chloride and phenylchlorothioformate, very preferably thiophosgene.

[0092] Another preferred route for the synthesis of isothiocyanates of formula D involves the reaction of N-hydroxycarboximidoyl chloride N2 with, for example, thiourea or a thiocarbonate.

[0093]

[0094] The compounds wherein the terminal groups X D It represents a compound of formula D of -C≡C-CN.

[0095] The preparation of the compound wherein the terminal group X is prepared according to the method described in MS Shvartsberg et al., Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1976), (10), 2292-5 (Scheme 6) D Compounds of formula D representing -C≡C-NCS: Acetylene 13 can be converted to chloride 14 by deprotonation and chlorination with N-chlorosuccinimide, which can be reacted with sodium amide to give amines of formula N-3, from which compounds of formula D (Scheme 6, D') can be obtained using known reagents such as those listed above.

[0096] In the reactions shown above and in Schemes 1 to 6 below, the reaction is exemplified for a compound of formula D, wherein the group express Obviously, the reaction can be carried out by choosing suitable reaction conditions or by, for example, first reacting compound 1a with a precursor G carrying a terminal group (Scheme 5) instead of a wing group R D The building blocks of express A compound of formula D.

[0097] Option 6:

[0098]

[0099] The reactions described should be regarded as illustrative only. A person skilled in the art can carry out corresponding variations of the syntheses described and also follow other suitable synthetic routes in order to obtain compounds of formula D.

[0100] In a preferred embodiment of the present invention, the compound of formula D is selected from the compounds of formula D-1 and D-2:

[0101]

[0102] The radicals occurring therein have the meanings given above for formula D, and

[0103] t2 is 0, 1, or 2,

[0104] t4 is 0 or 1,

[0105] And t2+t4 is 1, 2 or 3, preferably 1 or 2.

[0106] In formula D and its subformulas,

[0107] and Preferred representation

[0108] where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms or cycloalkyl having 3 to 5 C atoms,

[0109] X D Indicates -NCS,

[0110] Z D1 , Z D2 , Z D3 and Z D4 represent, identically or differently, -CH=CH-, -CF=CF-, -C≡C- or a single bond,

[0111] in

[0112] Alternatively expressed

[0113] in

[0114] W represents N, CH, CF or C-Cl, and

[0115] Y 1 and Y 2 represents H, Cl, F, methyl or ethyl, identically or differently.

[0116] In formulae D-1 and D-2, t2 and t4 are preferably 0 or 1, wherein t2+t4 is 1 or 2.

[0117] Preferred compounds of formula D-1 are selected from the following sub-formulas:

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] where R D 、X D 、 and has the meaning defined above, and preferably

[0124] R D represents a straight-chain alkyl or alkoxy group having 1 to 12 C atoms, or a straight-chain alkenyl or alkynyl or alkenyloxy or alkynyloxy group having 2 to 12 C atoms, or a branched or cyclic alkyl or alkoxy or alkenyl or alkenyloxy group having 3 to 12 C atoms, more preferably a straight-chain alkyl group having 1 to 7 C atoms or an alkynyl group having 2 to 7 C atoms,

[0125] X D represents NCS, and

[0126] express wherein Y represents identically or differently F, Cl or CH3, preferably F.

[0127] More preferably

[0128] L represents, identically or differently on each occurrence, F, Cl, CH3 or C2H5, and

[0129] n is 1 or 2, preferably 1.

[0130] Very preferred are compounds of formula D-1-1, D-1-2, D-1-3, D-1-4, D-1-9, D-1-10, D-1-11, D-1-12, D-2-1, D-2-2, D-2-3, D-2-4, D-2-9, D-2-10, D-2-11 and D-2-12.

[0131] In a preferred embodiment, the medium according to the invention comprises one or more compounds selected from the group of compounds of the formulae I, II and III:

[0132]

[0133] in

[0134] R 1 represents H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, wherein one or more CH2- groups may be replaced by Instead, preferably represents a non-fluorinated alkyl group or a non-fluorinated alkenyl group,

[0135] n is 0, 1, or 2,

[0136] to

[0137] Indicates that each occurrence is independent of the other

[0138]

[0139] where R L represents, identically or differently on each occurrence, H or an alkyl radical having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H,

[0140] or

[0141] wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F,

[0142] and among them

[0143] Alternatively,

[0144]

[0145] Preferred

[0146]

[0147] And when n=2, One of the preferred representations and the other preferably represents

[0148]

[0149] or One of the preferred representations and another preferably represents

[0150]

[0151] Preferably

[0152] to

[0153] Independently express

[0154]

[0155] More preferably

[0156] express

[0157] express

[0158] express

[0159] R 2 represents H, a non-fluorinated alkyl or non-fluorinated alkoxy radical having 1 to 17, preferably 2 to 10, C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl radical having 2 to 15, preferably 3 to 10, C atoms, wherein one or more CH2- radicals may be replaced by Instead, preferably represents a non-fluorinated alkyl group or a non-fluorinated alkenyl group,

[0160] Z 21 represents trans-CH=CH-, trans-CF=CF- or -C≡C-, preferably represents -C≡C- or trans-CH=CH-, and

[0161] and

[0162] Independently express

[0163]

[0164] where R L represents, identically or differently on each occurrence, H or an alkyl radical having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H,

[0165] or

[0166] wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F,

[0167] Preferably

[0168] and

[0169] Independently express

[0170]

[0171] Preferred representation

[0172] and

[0173] Preferred representation

[0174]

[0175] More preferred

[0176]

[0177] R 3 represents H, a non-fluorinated alkyl or non-fluorinated alkoxy radical having 1 to 17, preferably 2 to 10, C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl radical having 2 to 15, preferably 3 to 10, C atoms, wherein one or more CH2- radicals may be replaced by Instead, preferably represents a non-fluorinated alkyl group or a non-fluorinated alkenyl group,

[0178] Z 31 and Z 32 One of them is preferably Z 32 ; represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other of which independently represents -C≡C-, trans-CH=CH-, trans-CF=CF- or a single bond, preferably one of them, preferably Z 32 represents -C≡C- or trans-CH=CH-, and the other represents a single bond, and

[0179] to

[0180] Independently express

[0181]

[0182] where R L represents, identically or differently on each occurrence, H or an alkyl radical having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H,

[0183] or

[0184] wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F,

[0185] And among them

[0186] Alternatively expressed

[0187] Preferably

[0188] to

[0189] Independently express

[0190]

[0191] More preferably

[0192] express

[0193] express

[0194] in particular

[0195] express

[0196] in particular

[0197] In the compounds of formula I, II and III, R L Preferably it represents H.

[0198] In another preferred embodiment, in the compounds of formulae I, II and III, one or two radicals R L , preferably a group R L Different from H.

[0199] In a preferred embodiment of the present invention, the compound of formula I is selected from the group of compounds of formulae I-1 to I-5:

[0200]

[0201] in

[0202] L 1 , L 2 and L 3 represents H or F in the same or different manner on each occurrence,

[0203] and the other groups have the corresponding meanings indicated above for formula I, and

[0204] Preferably,

[0205] R 1 represents a non-fluorinated alkyl group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms.

[0206] Preferably, the medium comprises one or more compounds selected from the compounds of formula Ia and optionally one or more compounds selected from the compounds of formula Cy-1,

[0207]

[0208] The radicals present therein have the meanings given above for formula I-1. The total amount of compounds of formula I-1 and / or Cy-1 in the medium according to the invention is less than 10%, more preferably less than 5%, and in particular less than 2%. Particularly preferably, the medium contains no compounds of formula Cy-1.

[0209] The medium preferably comprises one or more compounds of the formula I-1, which are preferably selected from the group of compounds of the formulae I-1a to I-1d, preferably of the formula I-1b:

[0210]

[0211] where R 1 has the meaning indicated above for formula I and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0212] The medium preferably comprises one or more compounds of the formula I-2, which are preferably selected from the group of compounds of the formulae I-2a to I-2e, preferably of the formula I-2c:

[0213]

[0214]

[0215] where R 1 has the meaning indicated above for formula I and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0216] The medium preferably comprises one or more compounds of the formula I-3, which are preferably selected from the group of compounds of the formulae I-3a to I-3d, particularly preferably the group of compounds of the formula I-3b:

[0217]

[0218] where R 1 has the meaning indicated above for formula I and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0219] The medium preferably comprises one or more compounds of the formula I-4, which are preferably selected from the group of compounds of the formulae I-4a to I-4e, particularly preferably the formula I-4b:

[0220]

[0221] where R 1 has the meaning indicated above for formula I and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0222] The medium preferably comprises one or more compounds of the formula I-5, which are preferably selected from the group of compounds of the formulae I-5a to I-5d, particularly preferably the group of compounds of the formula I-5b:

[0223]

[0224]

[0225] where R 1 has the meaning indicated above for formula I and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0226] The medium preferably comprises one or more compounds of formula II, which are preferably selected from the group of compounds of formulae II-1 to II-3, preferably from the group of compounds of formulae II-1 and II-2:

[0227]

[0228] The radicals occurring therein have the meanings given above under formula II, and

[0229] Preferably,

[0230] R 2 represents a non-fluorinated alkyl or alkoxy group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms,

[0231] and

[0232] and One of them said

[0233]

[0234] and the other independently expresses

[0235]

[0236] Preferably

[0237]

[0238] Most preferably

[0239]

[0240] And preferably,

[0241] R 2 Indicates C n H 2n+1 or CH2=CH-(CH2) Z ,and

[0242] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0243] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0244] The compound of formula II-1 is preferably selected from the group of compounds of formulae II-1a to II-1e:

[0245]

[0246]

[0247] in

[0248] R 2 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,and

[0249] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0250] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0251] The compound of formula II-2 is preferably selected from the group of compounds of formula II-2a and II-2b:

[0252]

[0253] in

[0254] R 2 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,

[0255] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0256] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0257] The compound of formula II-3 is preferably selected from the group of compounds of formulae II-3a to II-3d:

[0258]

[0259]

[0260] in

[0261] R 2 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,

[0262] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0263] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0264] The compound of formula III is preferably selected from the group of compounds of formulae III-1 to III-6, more preferably selected from the group of compounds of formulae III-1, III-2, III-3 and III-4, and especially preferably the group of compounds of formula III-1:

[0265]

[0266]

[0267] in

[0268] Z 31 and Z 32 represents, independently of each other, trans-CH=CH- or trans-CF=CF-, preferably trans-CH=CH-, and in formula III-6, alternatively Z 31 and Z 32 One of them may represent -C≡C- and the other group has the meaning given above for formula III,

[0269] And preferably,

[0270] R 3 represents a non-fluorinated alkyl or alkoxy group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms,

[0271] and

[0272] to One, preferably express

[0273]

[0274] Very good

[0275]

[0276] and the others are expressed independently of each other

[0277]

[0278]

[0279] Preferably

[0280]

[0281] More preferred

[0282]

[0283] in

[0284] Alternatively,

[0285] And preferably,

[0286] R 3 Indicates C n H 2n+1 or CH2=CH-(CH2) Z ,

[0287] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0288] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0289] The compound of formula III-1 is preferably selected from the group of compounds of formulae III-1a to III-1j, more preferably selected from the group of compounds of formulae III-1a, III-1b, III-1g and III-1h, and particularly preferably the group of compounds of formulae III-1b and / or III-1h:

[0290]

[0291]

[0292]

[0293] in

[0294] R 3 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,

[0295] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0296] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0297] The compound of formula III-2 is preferably a compound of formula III-2a to III-21, very preferably III-2b and / or III-2j:

[0298]

[0299]

[0300] in

[0301] R 3 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,

[0302] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0303] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0304] The compound of formula III-5 is preferably selected from the compounds of formula III-5a:

[0305]

[0306] R 3 has the meaning indicated above for formula III-5 and preferably represents C n H 2n+1 ,in

[0307] n represents an integer within the range of 1 to 7, preferably within the range of 2 to 6.

[0308] In a preferred embodiment of the present invention, the medium comprises one or more compounds of the formula III selected from the group consisting of formulae IIIa-1 to IIIa-4:

[0309]

[0310] where R 3 has the meaning defined for formula III and preferably represents a straight-chain alkyl radical having 1 to 7 C atoms or a branched-chain alkyl radical having 1 to 9 C atoms, wherein one or more CH2- radicals may be replaced by Alternative.

[0311] Very preferred are compounds of the formulae IIIa-2 and IIIa-3.

[0312] In a preferred embodiment, the medium according to the invention comprises one or more compounds selected from the group of compounds of the formulae IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2:

[0313]

[0314]

[0315] in

[0316] R 1 represents an alkyl or alkenyl group having up to 7 C atoms, preferably ethyl, n-propyl, n-butyl or n-pentyl, n-hexyl,

[0317] R L represents, identically or differently on each occurrence, an alkyl or alkenyl radical having 1 to 5 C atoms or a cycloalkyl or cycloalkenyl radical having 3 to 6 C atoms, preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl, very preferably ethyl,

[0318] And the compound of formula II-1 is not included therein.

[0319] Furthermore, in a certain embodiment, the liquid-crystalline medium according to the invention, which may be the same as or different from the previously preferred embodiments, preferably comprises one or more compounds of the formula IV,

[0320]

[0321] in

[0322] express

[0323]

[0324] s is 0 or 1, preferably 1, and

[0325] Preferably,

[0326] express

[0327] Especially preferred

[0328]

[0329] L 4represents H or alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6 C atoms or cycloalkenyl having 4 to 6 C atoms, preferably CH3, C2H5, n-C3H7, i-C3H7, cyclopropyl, cyclobutyl, cyclohexyl, cyclopent-1-enyl or cyclohex-1-enyl, and particularly preferably CH3, C2H5, cyclopropyl or cyclobutyl,

[0330] X 4 represents H, alkyl having 1 to 3 C atoms or halogen, preferably H, F or Cl, more preferably H or F and very especially preferably F,

[0331] R 41 to R 44 represents, independently of one another, a non-fluorinated alkyl or non-fluorinated alkoxy group each having 1 to 15 C atoms, a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl group each having 2 to 15 C atoms, or a cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl group each having up to 15 C atoms, and alternatively R 43 and R 44 One or both of them also represent H,

[0332] Preferably,

[0333] R 41 and R 42 independently of one another represent a non-fluorinated alkyl group or a non-fluorinated alkoxy group each having 1 to 7 C atoms, or a non-fluorinated alkenyl group, a non-fluorinated alkenyloxy group or a non-fluorinated alkoxyalkyl group each having 2 to 6 C atoms,

[0334] Particularly preferably,

[0335] R 41 represents a non-fluorinated alkyl group having 1 to 7 C atoms or a non-fluorinated alkenyl group, a non-fluorinated alkenyloxy group or a non-fluorinated alkoxyalkyl group each having 2 to 6 C atoms, and

[0336] Particularly preferably,

[0337] R 42 represents a non-fluorinated alkyl group or a non-fluorinated alkoxy group each having 1 to 7 C atoms, and

[0338] Preferably,

[0339] R 43 and R 44represents H, non-fluorinated alkyl having 1 to 5 C atoms, non-fluorinated cycloalkyl or cycloalkenyl having 3 to 7 C atoms, non-fluorinated alkylcyclohexyl or non-fluorinated cyclohexylalkyl having 4 to 12 C atoms, or non-fluorinated alkylcyclohexylalkyl having 5 to 15 C atoms, particularly preferably cyclopropyl, cyclobutyl or cyclohexyl, and very particularly preferably, R 43 and R 44 At least one of them represents an n-alkyl group, particularly preferably a methyl group, an ethyl group or an n-propyl group, and the other represents H or an n-alkyl group, particularly preferably H, a methyl group, an ethyl group or an n-propyl group.

[0340] Very preferably, the compound of formula IV is selected from the compound of formula IV-1

[0341]

[0342] where R 41 and R 42 Identically or differently represent alkyl radicals having 2, 3, 4, 5 or 6 C atoms.

[0343] In a preferred embodiment of the present invention, the liquid-crystalline medium additionally comprises one or more compounds selected from the group of compounds of the formulae V, VI, VII, VIII and IX:

[0344]

[0345] in

[0346] L 51 Represents R 51 or X 51 ,

[0347] L 52 Represents R 52 or X 52 ,

[0348] R 51 and R 52 independently of one another represent H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or non-fluorinated alkenyl,

[0349] X 51 and X 52 independently of one another represent H, F, Cl, -CN, SF5, a fluorinated alkyl group or a fluorinated alkoxy group having 1 to 7 C atoms, or a fluorinated alkenyl group, a fluorinated alkenyloxy group or a fluorinated alkoxyalkyl group having 2 to 7 C atoms, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F or Cl, and

[0350] to

[0351] Independently express

[0352]

[0353] Preferably

[0354]

[0355] L 61 Represents R 61 , and in Z 61 and / or Z 62 In the case of trans-CH=CH- or trans-CF=CF-, X is also represented instead. 61 ,

[0356] L 62 Represents R 62 , and in Z 61 and / or Z 62 In the case of trans-CH=CH- or trans-CF=CF-, X is also represented instead. 62 ,

[0357] R 61 and R 62 independently of one another represent H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or non-fluorinated alkenyl,

[0358] X 61 and X 62 independently of one another represent F or Cl, -CN, SF5, a fluorinated alkyl or alkoxy group having 1 to 7 C atoms, or a fluorinated alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 7 C atoms,

[0359] Z 61 and Z 62 One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C- and the other one thereof independently represents trans-CH=CH-, trans-CF=CF- or a single bond, preferably, one of them represents -C≡C- or trans-CH=CH- and the other one represents a single bond, and

[0360]

[0361] to

[0362] Independently express

[0363]

[0364] Preferably

[0365]

[0366] and

[0367] x represents 0 or 1;

[0368] L 71 Represents R 71 or X 71 ,

[0369] L 72 Represents R 72 or X 72 ,

[0370] R 71 and R 72 independently of one another represent H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or non-fluorinated alkenyl,

[0371] X 71 and X 72 independently of one another represent H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl group or a fluorinated alkoxy group having 1 to 7 C atoms, or a fluorinated alkenyl group, a non-fluorinated or fluorinated alkenyloxy group or a non-fluorinated or fluorinated alkoxyalkyl group having 2 to 7 C atoms, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F or Cl, and

[0372] Z 71 to Z 73 independently of one another represent trans-CH=CH-, trans-CF=CF-, -C≡C- or a single bond, preferably, one or more of them represent a single bond, particularly preferably, all represent a single bond, and

[0373] to

[0374] Independently express

[0375]

[0376] Preferably

[0377]

[0378] R 81 and R 82independently of one another represent H, a non-fluorinated alkyl or alkoxy group having 1 to 15, preferably 2 to 10, C atoms, or a non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 15, preferably 3 to 10, C atoms, preferably a non-fluorinated alkyl or alkenyl group,

[0379] Z 81 and Z 82 One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C- and the other one thereof independently represents trans-CH=CH-, trans-CF=CF- or a single bond, preferably, one of them represents -C≡C- or trans-CH=CH- and the other one represents a single bond, and

[0380] express

[0381]

[0382] and

[0383] Independently express

[0384]

[0385] L 91 Represents R 91 or X 91 ,

[0386] L 92 Represents R 92 or X 92 ,

[0387] R 91 and R 92 independently of one another represent H, a non-fluorinated alkyl or alkoxy group having 1 to 15, preferably 2 to 10, C atoms, or a non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 15, preferably 3 to 10, C atoms, preferably a non-fluorinated alkyl or alkenyl group,

[0388] X 91 and X 92 independently of one another represent H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl group or a fluorinated alkoxy group having 1 to 7 C atoms, or a fluorinated alkenyl group, a non-fluorinated or fluorinated alkenyloxy group or a non-fluorinated or fluorinated alkoxyalkyl group having 2 to 7 C atoms, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F or Cl, and

[0389] Z 91 to Z 93independently of one another represent trans-CH=CH-, trans-CF=CF-, -C≡C- or a single bond, preferably one or more of them represent a single bond, and particularly preferably all represent a single bond,

[0390] express

[0391]

[0392] to

[0393] Independently express

[0394]

[0395] In a preferred embodiment of the present invention, the liquid-crystalline medium comprises one or more compounds of the formula V, which are preferably selected from the group of compounds of the formulae V-1 to V-3, preferably of the formulae V-1 and / or V-2 and / or V-3, preferably of the formulae V-1 and V-2:

[0396]

[0397] The radicals occurring therein have the corresponding meanings indicated above for formula V and are preferably

[0398] R 51 represents a non-fluorinated alkyl group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms,

[0399] R 52 represents a non-fluorinated alkyl group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms or a non-fluorinated alkoxy group having 1 to 7 C atoms,

[0400] X 51 and X 52 Each independently represents F, Cl, -OCF3, -CF3, -CN or -SF5, preferably F, Cl, -OCF3 or -CN.

[0401] The compound of formula V-1 is preferably selected from the group of compounds of formulae V-1a to V-1d, preferably V-1c and V-1d:

[0402]

[0403] wherein the parameters have the corresponding meanings indicated above for formula V-1, and wherein

[0404] Y 51 and Y 52 represents H or F in each case independently of one another, and preferably

[0405] R 51 represents an alkyl group or an alkenyl group, and

[0406] X 51 It represents F, Cl or -OCF3.

[0407] The compound of formula V-2 is preferably selected from the group of compounds of formulae V-2a to V-2e and / or from the group of compounds of formulae V-2f and V-2g:

[0408]

[0409]

[0410] wherein in each case, the compound of formula V-2a is not included in the compounds of formulae V-2b and V-2c, the compound of formula V-2b is not included in the compounds of formula V-2c, and the compound of formula V-2f is not included in the compounds of formula V-2g, and

[0411] wherein the parameters have the corresponding meanings indicated above for formula V-1, and wherein

[0412] Y 51 and Y 52 represents, independently of each other, H or F in each case, and

[0413] Preferably,

[0414] Y 51 and Y 52 represents H and the other represents H or F, preferably both represent H.

[0415] The compound of formula V-3 is preferably a compound of formula V-3a:

[0416]

[0417] wherein the parameters have the corresponding meanings indicated above for formula V-1, and wherein preferably X 51 represents F, Cl, preferably F,

[0418] X 52 represents F, Cl or -OCF3, preferably -OCF3.

[0419] The compound of formula V-1a is preferably selected from the group of compounds of formula V-1a-1 and V-1a-2:

[0420]

[0421] in

[0422] R 51 has the meaning indicated above and preferably represents C n H2n+1 ,in

[0423] n represents an integer in the range of 1-7, preferably in the range of 1-6 and particularly preferably 3-5.

[0424] The compound of formula V-1b is preferably a compound of formula V-1b-1:

[0425]

[0426] in

[0427] R 51 has the meaning indicated above and preferably represents C n H 2n+1 ,in

[0428] n represents an integer in the range of 1-7, preferably in the range of 1-6 and particularly preferably 3-5.

[0429] The compound of formula V-1c is preferably selected from the group of compounds of formulae V-1c-1 to V-1c-4, particularly preferably selected from the group of compounds of formulae V-1c-1 and V-1c-2:

[0430]

[0431] in

[0432] R 51 has the meaning indicated above and preferably represents C n H 2n+1 ,in

[0433] n represents an integer in the range of 1-7, preferably in the range of 1-6 and particularly preferably 3-5.

[0434] The compound of formula V-1d is preferably selected from the group of compounds of formula V-1d-1 and V-1d-2, particularly preferably the compound of formula V-1d-2:

[0435]

[0436] in

[0437] R 51 has the meaning indicated above and preferably represents C n H 2n+1 ,in

[0438] n represents an integer in the range of 1-7, preferably in the range of 1-6 and particularly preferably 3-5.

[0439] The compound of formula V-2a is preferably selected from the group of compounds of formula V-2a-1 and V-2a-2, particularly preferably the compound of formula V-2a-1:

[0440]

[0441] wherein

[0442] R 51 have the meaning indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0443] R 52 have the meaning indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0444] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and especially preferably 3 to 5, and

[0445] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0446] R 51 with the preferred combinations of R 52 , especially in the case of formula V-2a-1, are (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and O-C m H 2m+1 ), (CH2=CH-(CH2) Z and C m H 2m+1 ), (CH2=CH-(CH2) Z and O-C m H 2m+1 ) and (C n H 2n+1 and (CH2) Z -CH=CH2).

[0447] Preferred compounds of the formula V-2b are compounds of the formula V-2b-1 :

[0448]

[0449] wherein

[0450] R 51 have the meaning indicated above and preferably denote C n H2n+1 or CH2=CH-(CH2) Z ,and

[0451] R 52 has the meaning indicated above and preferably represents C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0452] n and m independently of one another represent an integer in the range of 1 to 7, preferably in the range of 1 to 6 and particularly preferably in the range of 3 to 5, and

[0453] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0454] In particular, R 51 With R 52 The preferred combination here is C n H 2n+1 and C m H 2m+1 .

[0455] A preferred compound of formula V-2c is a compound of formula V-2c-1:

[0456]

[0457] in

[0458] R 51 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,and

[0459] R 52 has the meaning indicated above and preferably represents C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0460] n and m independently of one another represent an integer in the range of 1 to 7, preferably in the range of 1 to 6 and particularly preferably in the range of 3 to 5, and

[0461] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0462] In particular, (R 51 and R 52 The preferred combination of ) is (C n H2n+1 and C m H 2m+1 ).

[0463] Preferred compounds of the formula V-2d are compounds of the formula V-2d-1 :

[0464]

[0465] wherein

[0466] R 51 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z and

[0467] R 52 have the meanings indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0468] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and

[0469] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0470] In particular, preferred combinations of (R 51 and R 52 ) here are (C n H 2n+1 and C m H 2m+1 ).

[0471] Preferred compounds of the formula V-2e are compounds of the formula V-2e-1 :

[0472]

[0473] wherein

[0474] R 51 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z and

[0475] R 52 have the meanings indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1or (CH2) Z -CH=CH2, and wherein

[0476] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0477] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0478] In particular, the preferred combinations of (R 51 and R 52 ) here are (C n H 2n+1 and O-C m H 2m+1 ).

[0479] Preferred compounds of the formula V-2f are compounds of the formula V-2f-1 :

[0480]

[0481] wherein

[0482] R 51 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0483] R 52 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0484] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0485] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0486] In particular, the preferred combinations of (R 51 and R 52 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), especially preferably (C n H 2n+1 and C m H2m+1 ).

[0487] Preferred compounds of the formula V-2g are compounds of the formula V-2g-1 :

[0488]

[0489] wherein

[0490] R 51 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0491] R 52 have the meanings indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0492] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0493] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0494] In particular, the preferred combinations of (R 51 and R 52 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and O-C m H 2m+1 ).

[0495] The compounds of the formula VI are preferably selected from the group of compounds of the formulae VI-1 to VI-5:

[0496]

[0497] wherein

[0498] Z 61 and Z 62represents -CºC-, trans-CH=CH- or trans-CF=CF-, preferably -CºC- or trans-CH=CH-, and the other occurring radicals and parameters have the meanings given above under formula VI,

[0499] and preferably,

[0500] R 61 and R 62 independently of one another represent H, an unfluorinated alkyl or alkoxy radical having 1 to 7 C atoms or an unfluorinated alkenyl radical having 2 to 7 C atoms,

[0501] X 62 represents F, Cl, -OCF3or -CN,

[0502] The compounds of the formula VI-1 are preferably selected from the group of compounds of the formulae VI-1 a and VI-1 b, more preferably from compounds of the formula VI-1 a:

[0503]

[0504] wherein

[0505] R 61 have the meanings indicated above and preferably represent C n H 2n+1 or CH2=CH-(CH2) Z and

[0506] R 62 have the meanings indicated above and preferably represent C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0507] n and m independently of one another represent an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0508] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0509] In particular, the preferred combinations of (R 61 and R 62 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H2n+1 and C m H 2m+1 ), and in the case of Formula VI-1b, it is particularly preferably (C n H 2n+1 and OC m H 2m+1 ).

[0510] The compound of formula VI-3 is preferably selected from the compounds of formulae VI-3a to VI-3e:

[0511]

[0512]

[0513] wherein the parameters have the meanings given above under formula VI-3, and preferably R 61 has the meaning indicated above and preferably represents C n H 2n+1 , wherein n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and X 62 It represents -F, -Cl, -OCF3 or -CN.

[0514] The compound of formula VI-4 is preferably selected from the compounds of formulae VI-4a to VI-4e:

[0515]

[0516]

[0517] wherein the parameters have the meanings given above under formula VI-4, and preferably R 61 has the meaning indicated above and preferably represents C n H 2n+1 , wherein n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and X 62 represents F, Cl, OCF3 or -CN.

[0518] The compound of formula VI-5 is preferably selected from the compounds of formulae VI-5a to VI-5d, preferably VI-5b:

[0519]

[0520]

[0521] wherein the parameters have the meanings given above under formula VI-5, and preferably R 61 has the meaning indicated above and preferably represents C n H 2n+1wherein n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 5, and X 62 represents -F, -CI, -OCF3 or -CN, especially preferably -OCF3.

[0522] The compounds of the formula VII are preferably selected from the group of compounds of the formulae VII-1 to VII-6:

[0523]

[0524]

[0525] wherein the compounds of the formula VII-5 are not included in the compounds of the formula VII-6, and

[0526] wherein the parameters have the respective meanings indicated above for the formula VII,

[0527] Y 71 , Y 72 , Y 73 independently of one another, denote H or F,

[0528] and preferably,

[0529] R 71 denote unfluorinated alkyl or alkoxy each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms,

[0530] R 72 denote unfluorinated alkyl or alkoxy each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms,

[0531] X 72 denote F, CI; NCS or -OCF3, preferably F or NCS, and

[0532] especially preferably,

[0533] R 71 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0534] R 72 have the meanings indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0535] n and m independently of one another denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0536] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0537] The compounds of the formula VII-1 are preferably selected from the group of compounds of the formulae VII-1 a to VII-1 d:

[0538]

[0539] wherein X 72 have the meanings given above for the formula VII-2, and

[0540] R 71 have the meanings indicated above and preferably denote C n H 2n+1 wherein

[0541] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0542] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2, and

[0543] X 72 preferably denotes F.

[0544] The compounds of the formula VII-2 are preferably selected from the group of compounds of the formulae VII-2a and VII-2b, especially preferably of the formula VII-2a:

[0545]

[0546] wherein

[0547] R 71 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0548] R 72 have the meanings indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0549] n and m independently of one another denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0550] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0551] In particular, preferred combinations of (R 71 and R 72 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), especially preferred are (C n H 2n+1 and C m H 2m+1 ).

[0552] The compound of the formula VII-3 is preferably a compound of the formula VII-3a:

[0553]

[0554] wherein

[0555] R 71 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0556] R 72 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0557] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0558] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0559] In particular, preferred combinations of (R 71 and R 72 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), especially preferred are (C n H 2n+1 and C m H 2m+1 ).

[0560] The compound of the formula VII-4 is preferably a compound of the formula VII-4a:

[0561]

[0562] wherein

[0563] R 71 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0564] R 72 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0565] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0566] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0567] In particular, the preferred combinations of (R 71 and R 72 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0568] The compound of the formula VII-5 is preferably selected from the group of compounds of the formulae VII-5a and VII-5b, more preferably of the formula VII-5a:

[0569]

[0570] wherein

[0571] R 71 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0572] R 72 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0573] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0574] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0575] In particular, the preferred combinations of (R 71 and R 72 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0576] The compounds of the formula VII-6 are preferably selected from the group of compounds of the formulae VII-6a and VII-6b:

[0577]

[0578] wherein

[0579] R 71 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0580] R 72 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0581] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0582] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0583] In particular, (R 71 and R 72 The preferred combination of ) is (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0584] The compound of formula VII-7 is preferably selected from the group of compounds of formulae VII-7a to VII-7d:

[0585]

[0586] in

[0587] R 71 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,

[0588] X 72 Indicates F, -OCF3 or -NCS,

[0589] n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0590] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0591] The compound of formula VIII is preferably selected from the group of compounds of formulae VIII-1 to VIII-3, more preferably these compounds of formula VIII consist essentially of them, even more preferably essentially of them and very especially preferably completely of them:

[0592]

[0593] in

[0594] Y 81 and Y 82 One of them represents H and the other represents H or F, and

[0595] R 81 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2)Z and

[0596] R 82 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0597] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0598] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0599] In particular, the preferred combinations of (R 81 and R 82 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0600] The compounds of the formula VIII-1 are preferably selected from the group of compounds of the formulae VIII-1 a to VIII-1 c:

[0601]

[0602] wherein

[0603] R 81 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0604] R 82 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0605] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0606] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0607] In particular, the preferred combinations of (R 81 and R 82 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), especially preferred are (C n H 2n+1 and C m H 2m+1 ).

[0608] The compounds of the formula VIII-2 are preferably compounds of the formula VIII-2a:

[0609]

[0610] wherein

[0611] R 81 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0612] R 82 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0613] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0614] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0615] In particular, the preferred combinations of (R 81 and R 82 ) here are (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and O-C m H 2m+1 ) and (CH2=CH-(CH2) Z and Cm H 2m+1 ), especially preferably (C n H 2n+1 and C m H 2m+1 ).

[0616] The compound of the formula VIII-3 is preferably a compound of the formula VIII-3a:

[0617]

[0618] wherein

[0619] R 81 has the meaning indicated above and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0620] R 82 has the meaning indicated above and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0621] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and especially preferably 3 to 5, and

[0622] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0623] In particular, the preferred combinations of (R 81 and R 82 ) here are (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ).

[0624] The compound of the formula IX is preferably selected from the group of compounds of the formulae IX-1 to IX-3:

[0625]

[0626] wherein the parameters have the respective meanings indicated above under formula IX, and preferably

[0627] to one of

[0628] denotes

[0629] And among them

[0630] R 91 has the meaning indicated above and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z ,and

[0631] R 92 has the meaning indicated above and preferably represents C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0632] n and m independently of one another represent an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0633] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0634] In particular, (R 91 and R 92 The preferred combination of ) is (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ).

[0635] The compound of formula IX-1 is preferably selected from the group of compounds of formulae IX-1a to IX-1e:

[0636]

[0637] wherein the parameters have the meanings given above and preferably

[0638] R 91 has the meaning indicated above and preferably represents C n H 2n+1 ,and

[0639] n represents an integer in the range of 0 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and

[0640] X 92 Preferably it represents F or Cl.

[0641] The compound of formula IX-2 is preferably selected from the group of compounds of formula IX-2a and IX-2b:

[0642]

[0643] wherein

[0644] R 91 have the meaning indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0645] R 92 have the meaning indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0646] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0647] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0648] In particular, the preferred combination of (R 91 and R 92 ) here is (C n H 2n+1 and C m H 2m+1 ).

[0649] The compounds of the formula IX-3 are preferably compounds of the formulae IX-3a and IX-3b:

[0650]

[0651] wherein

[0652] R 91 have the meaning indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0653] R 92 have the meaning indicated above and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0654] n and m independently of one another represent an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and

[0655] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0656] In particular, (R 91 and R 92 The preferred combination of ) is (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and OC m H 2m+1 ).

[0657] In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula X

[0658]

[0659] in

[0660] R 101 represents H, alkyl or alkoxy having 1 to 15, preferably 2 to 10, C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or alkenyl,

[0661] X 101 represents H, F, Cl, -CN, SF5, NCS, a fluorinated alkyl group or a fluorinated alkoxy group having 1 to 7 C atoms, or a fluorinated alkenyl group, a fluorinated alkenyloxy group or a fluorinated alkoxyalkyl group having 2 to 7 C atoms, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F, Cl or NCS, particularly preferably NCS,

[0662] Y 101 represents methyl, ethyl or Cl,

[0663] Y 102 represents H, methyl, ethyl, F or Cl, preferably H or F,

[0664] Z 101 , Z 102 represent, identically or differently, a single bond, -CH=CH-, -CF=CF- or -C≡C-,

[0665]

[0666] independently of one another

[0667]

[0668] preferably

[0669]

[0670] and wherein

[0671] alternatively and

[0672] n is 0 or 1.

[0673] Preferably, the compound of formula X is selected from the group of subformulae X-1 and X-2

[0674]

[0675] wherein the radicals and parameters occurring have the meanings given hereinbefore for formula X.

[0676] Especially preferably, the medium according to the application comprises one or more compounds selected from the group of compounds of formulae X-1-1 to X-1-9

[0677]

[0678] wherein R 101 represents an alkyl group having 1 to 7 C atoms.

[0679] In a preferred embodiment, the medium according to the application comprises one or more compounds of formula XI

[0680]

[0681] wherein

[0682] R S represents H, an alkyl or alkoxy group having 1 to 12 C atoms, or an alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 12 C atoms, wherein one or more CH2-groups can be replaced by alternatively, and wherein one or more H atoms can be replaced by F,

[0683]

[0684] independently of one another in each occurrence

[0685]

[0686] wherein R L in each occurrence identically or differently

[0687] H, Cl or a linear, branched or cyclic alkyl group having 1 to 6 C atoms,

[0688] L S1 , L S2 represent, identically or differently, H, Cl or F,

[0689] R S1 、R S2 identically or differently represent H, alkyl or alkenyl having up to 6 C atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl,

[0690] R Th1 、R Th2 identically or differently represent H, alkyl or alkenyl or alkoxy having up to 6 C atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl,

[0691] Z S1 , Z S2 , Z S3 represent, identically or differently, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C-, or a single bond,

[0692] a and b are the same or different and are 0 or 1.

[0693] Preferably, the compound of formula XI is selected from the group of compounds of formulae XI-1 to XI-24:

[0694]

[0695]

[0696]

[0697]

[0698] The radicals occurring therein have the meanings given above for formula XI and are preferably

[0699] R S represents an alkyl or alkenyl group having 2 to 6 C atoms, wherein one or more CH2- groups may be Alternative,

[0700] R S1 and R S2 identically or differently represent H or an alkyl group having 1 to 6 C atoms, preferably H,

[0701] R S3 represents H, F or alkyl with up to 6 C atoms, or cyclopropyl, preferably H, F or ethyl, very preferably H,

[0702] L S1 and L S2 identically or differently denote H or F, preferably F.

[0703] Preferably, the medium comprises one or more compounds of the formula XII

[0704]

[0705] wherein

[0706] R 12 denote H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CH2-groups can be replaced by or denote the group R P ,

[0707] R P denote halogen, CN, NCS, R F , R F -O- or R F -S-, wherein

[0708] R F denote fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms,

[0709] Z 121 , Z 122 identically or differently denote -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, preferably -C≡C- or a single bond,

[0710] X 1 , X 2 ,

[0711] X 3 and X 4 identically or differently denote Cl or F, preferably F,

[0712] t is 0 or 1, and

[0713] and

[0714] denote a group selected from the following group:

[0715] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by L, with the proviso that tetrafluoro-1,4-phenylene is excluded,

[0716] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1 ]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2groups can be replaced by -O- and / or -S- and wherein one or more H atoms can be replaced by F,

[0717] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, each of which can also be mono- or poly-substituted by L,

[0718] L, on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF5 or linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms which is in each case optionally fluorinated,

[0719] and wherein the compounds of formula XII are not included in the compounds of formulae I, II and III.

[0720] The compounds of formula XII are preferably selected from the group of the compounds of the subformulae XII-1 to XII-11 :

[0721]

[0722]

[0723]

[0724] wherein

[0725] L 1 , L 2 and L 3 identically or differently, denote H, F, Cl, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and

[0726] R 12 , X 1 , X 2 , X 3 and X 4 have the meanings given above for formula XII.

[0727] Very preferably, the medium comprises a compound of formula XII-3, wherein the occurring groups have the meanings given above, and especially preferably L 1 denotes H, X 1 , X 2 , X 3 and X 4 denote F, and R12 represents an alkyl group having 1 to 7 C atoms.

[0728] The medium according to the invention preferably comprises one or more compounds of the formula XIII

[0729]

[0730] in

[0731] R 13 represents H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, wherein one or more CH2- groups may be replaced by Replacement, or represents the group R P ,

[0732] R P Indicates halogen, CN, NCS, R F 、R F -O- or R F -S-, where

[0733] R F represents a fluorinated alkyl or fluorinated alkenyl group having up to 9 C atoms,

[0734] Z 131 , Z 132 , Z 133 represent, identically or differently, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or a single bond, preferably -C≡C- or a single bond,

[0735] X 1 、X 2 Identically or differently represent H, Cl, F, CH3 or C2H5, preferably H or F,

[0736] Y 1 、Y 2 、Y 3 、Y 4 represents, identically or differently, H, F, Cl or a linear, branched or cyclic alkyl, alkenyl, alkoxy or alkenyloxy group each having up to 12 carbon atoms, wherein Y 1 、Y 2 、Y 3 and Y 4 At least one of them is different from F,

[0737] s is 0, 1 or 2, preferably 0 or 1,

[0738] t is 0, 1 or 2, preferably 0 or 1, and

[0739] s +t is 0, 1 or 2, preferably 0 or 1,

[0740] and

[0741] denotes a radical selected from the group consisting of

[0742] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6- naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by L,

[0743] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1 ]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2groups can be replaced by -O- and / or -S- and wherein one or more H atoms can be replaced by F,

[0744] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, each of which can also be mono- or poly-substituted by L,

[0745] L denotes, on each occurrence, identically or differently, F, Cl, CN, SCN, SF5 or linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms which is in each case optionally fluorinated.

[0746] In a preferred embodiment of the present application, the compound of formula XIII is selected from the group consisting of compounds of formulae XIII-1 to XIII-20, very preferably from the group consisting of compounds of formulae XIII-1 to XIII-13:

[0747]

[0748]

[0749]

[0750]

[0751] wherein the occurring radicals have the meanings indicated above for formula XIII and its subformulae, and preferably, R 13 denotes alkyl having 1 to 7 C atoms, Y 1 , Y 2 , Y 3 and Y 4identically or differently H, F, CI, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and more preferably Y 1 and Y 2 independently H or F, in particular H, and Y 3 and Y 4 very preferably H, and L 1 and L 2 identically or differently very preferably H, F, methyl or ethyl, in particular H.

[0752] Preferably, the medium according to the application comprises one or more compounds of the formula T,

[0753]

[0754] wherein

[0755] R T denotes halogen, CN, NCS, R F , R F -O- or R F -S-, wherein

[0756] R F denotes fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms,

[0757] and

[0758] in each occurrence independently of one another

[0759]

[0760] L 4 and L 5 identically or differently F, CI or straight-chain or branched or cyclic alkyl or alkenyl having up to 12 C atoms each;

[0761] Z T3 , Z T4 identically or differently -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, and

[0762] t is 0 or 1.

[0763] In one preferred embodiment, the liquid-crystalline medium according to the application comprises one or more compounds selected from the group of compounds of the following formulae T-1a to T-3b:

[0764]

[0765] wherein

[0766] and has the meaning given above, and

[0767] n is 1, 2, 3, 4, 5, 6 or 7, preferably 1, 2, 3 or 4, and particularly preferably 1.

[0768] In a particularly preferred embodiment of the present invention, the medium comprises one or more compounds selected from the group consisting of compounds of the formulae T-1a and T-2a.

[0769] Preferred compounds of formula T-1a are selected from the group of compounds of the following sub-formulae:

[0770]

[0771] wherein n is 1, 2, 3 or 4, preferably 1.

[0772] Preferred compounds of formula T-2a are selected from the group of compounds of the following sub-formulas:

[0773] wherein n is 1, 2, 3 or 4, preferably 1.

[0774] Preferred compounds of formula T-3a are selected from the group of compounds of the following sub-formulas:

[0775]

[0776] wherein n is 1, 2, 3 or 4, preferably 1.

[0777] Very preferably, the medium according to the invention comprises one or more compounds of the formula T-1a-5.

[0778] In one embodiment, the medium according to the invention comprises one or more compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, in which the radical R 1 、R 2 、R 3 、R 41 、R 42 、R 51 、R 52 、R 61 、R 62 、R 71 、R 72 、R 81 、R 82 、R 91 、R 92 、R 101 、R 102 and R S are cyclic alkyl groups.

[0779] Very preferred compounds comprising a cyclic alkyl group are selected from the group consisting of compounds of formulae Cy-1 to Cy-14

[0780]

[0781]

[0782] In a preferred embodiment, the medium according to the application comprises a compound of formula N,

[0783]

[0784] wherein

[0785] R N represents H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, wherein one or more CH2-groups can be replaced by R P ,

[0786] R P represents halogen, CN, NCS, R F , R F -O- or R F -S-, wherein

[0787] R F represents fluorinated alkyl having 1 to 9 C atoms or fluorinated alkenyl having 2 to 9 C atoms,

[0788] Z N1 and Z N2 identically or differently represent -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, preferably -C≡C- or a single bond,

[0789] W represents N, C-F or C-Cl,

[0790] X 1 and X 2 identically or differently represent H, Cl, F, methyl or ethyl,

[0791] and

[0792] represents a group selected from the group consisting of:

[0793] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by L,

[0794] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2groups can be replaced by -O- and / or -S- and wherein one or more H atoms can be replaced by F,

[0795] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl or selenophene-2,5-diyl, each of which can also be substituted by R L monosubstituted or polysubstituted,

[0796] L denotes, on each occurrence, identically or differently, F, Cl, CN, SCN, SF5 or in each case optionally fluorinated linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, and

[0797] n is 0, 1 or 2.

[0798] The compounds of the formula N are preferably selected from the group consisting of formulae N-1, N-2 and N-3:

[0799]

[0800] wherein R N , Z N1 , Z N2 , X 1 , X 2 and n have the respective meanings given above for formula N.

[0801] In formula N and its subformulae N-1, N-2 and N-3, preferably and denote, on each occurrence, identically or differently,

[0802] wherein

[0803] R L denote, on each occurrence, identically or differently, H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H,

[0804] L denotes F or alkyl having 1 to 6 C atoms, and

[0805] r is 0, 1, 2, 3, 4, 5 or 6, preferably 0 or 1,

[0806] wherein Alternatively,

[0807] In a preferred embodiment, in formula N and its subformulae, the group X 1 and X 2 Both represent H.

[0808] In a preferred embodiment, in formula N and its subformulae, the group X 1 represents H and group X 2 Indicates F or Cl.

[0809] In a preferred embodiment, in formula N and its subformulae, the group X 1 represents F or Cl and the group X 2 Indicates H.

[0810] In a preferred embodiment, in formula N and its subformulae, the group X 1 and X 2 represents F or Cl, preferably both represent F.

[0811] The compounds of formula N-1, N-2 and N-3 are preferably selected from the group consisting of formulae N-1-1 to N-1-10, N-2-1 to N-2-10 and N-3-1 to N-3-10:

[0812]

[0813]

[0814]

[0815]

[0816]

[0817]

[0818] where R N 、X 1 and X 2 has the meanings given above, and L, identically or differently on each occurrence, represents H, F, methyl, ethyl or cyclopropyl.

[0819] In a preferred embodiment, the medium according to the invention comprises a compound of the formula NI

[0820]

[0821] in

[0822] R N 、 ZN1 , Z N2 , W, X 1 , X 2 and n have the respective meanings given in claim 1 for formula N.

[0823] The compounds of formula NI are preferably selected from the group consisting of compounds of formulae NI-1 and NI-2

[0824]

[0825] wherein R N , Z N1 , Z N2 , and have the meanings given above for formula N, Y 1 and Y 2 identically or differently, denote H, F or CI, and t is 0 or 1.

[0826] In the compounds of formula NI or NI-1 or NI-2, and preferably, independently of each other, denote

[0827] wherein

[0828] alternatively denote

[0829] and

[0830] L 1 and L 2 identically or differently, denote F, CI or straight-chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms.

[0831] In the compounds of formula NI or NI-1 or NI-2, Z N1 and Z N2 identically or differently, preferably denote -CºC- or a single bond.

[0832] In a preferred embodiment of the present application, the compounds of formulae NI-1 and NI-2 are selected from the group consisting of compounds of formulae NI-1-1 to NI-1-12 and NI-2-1 to NI-2-12:

[0833]

[0834]

[0835]

[0836]

[0837] wherein

[0838] L 1 , L 2 and L 3 identically or differently, denote H, F, CI, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and

[0839] R N , Y 1 and Y 2 have the meanings given above for formulae N-1 and N-2, and wherein very preferably the group denotes

[0840]

[0841] In a preferred embodiment, in the compounds of formula NI and the subformulae thereof, one or both, preferably both, of Y 1 and Y 2 denote H.

[0842] In another preferred embodiment, in the compounds of formula N and the subformulae thereof, both of Y 1 and Y 2 denote F.

[0843] Preferably, the medium according to the application comprises one or more compounds of formula UI

[0844]

[0845] wherein

[0846] R U denotes H, a straight-chain or branched, non-fluorinated alkyl group having 1 to 12 C atoms or a non-fluorinated alkenyl group having 2 to 12 C atoms, wherein one or more CH2-groups can be replaced by

[0847] wherein one or more non-adjacent CH2-groups can be replaced by O, or denotes a group R P ,

[0848] R P denotes halogen, CN, NCS, a fluorinated alkyl group, R F -O- or R F -S-, wherein

[0849] R F denotes a fluorinated alkyl group or a fluorinated alkenyl group having up to 9 C atoms,

[0850] Z U1represents -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or -C≡C-C≡C-, preferably -CF=CF- or -C≡C-,

[0851] X U1 , X U2 identically or differently, represent Cl or F, preferably F.

[0852] and

[0853] represents a radical selected from the group of:

[0854] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by L,

[0855] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups can be replaced by N, one or more non-adjacent CH2 groups can be replaced by -O- and / or -S-, and wherein one or more H atoms can be replaced by L,

[0856] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, each of which can also be mono- or poly-substituted by L,

[0857] L, on each occurrence, identically or differently, represents F, Cl, CN, SCN, SF5 or in each case straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms each which are optionally fluorinated,

[0858] u is 0 or 1,

[0859] v is 0 or 1,

[0860] with the proviso that and does not represent 1,4-phenylene which is optionally fluorinated, and wherein the compounds of formula UI and its subformulae are not included within the compounds of formula I, II and III.

[0861] The compounds of formula UI are preferably selected from the group of compounds consisting of formulae UI-1, UI-2 and UI-3:

[0862]

[0863] wherein R U , X U1 and X U2 have the meanings given above for formula UI, and wherein in formula UI-3 at least one of and denotes trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1 ]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups can be replaced by N, one or more non-adjacent CH2 groups can be replaced by -O- and / or -S- and wherein one or more H atoms can be replaced by L, wherein

[0864] L, on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF5 or in each case straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 12 C atoms which are optionally fluorinated in each case,

[0865] and preferably

[0866] X U1 and X U2 denote F, R U preferably denotes straight-chain or branched or cyclic alkyl or alkenyl having 1 to 7 C atoms or fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, and

[0867] identically or differently preferably denotes wherein R L on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms,

[0868] or denotes wherein one or more H atoms can be replaced by alkyl having 1 to 6 C atoms or by F.

[0869] very preferably denotes

[0870] preferably denotes more preferably is

[0871] Very particularly preferred are

[0872] wherein

[0873] R L denotes H or alkyl having 1 to 6 C atoms.

[0874] Preferred compounds of formula UI are selected from the following subformulae:

[0875]

[0876]

[0877] wherein R U have the meaning given above and preferably denote linear or branched alkyl having 1 to 7 C atoms, in particular methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0878] The liquid-crystalline medium according to the application preferably comprises one or more compounds of formula UII

[0879]

[0880] wherein

[0881] R U denotes H, linear or branched alkyl having 1 to 12 C atoms or alkenyl having 2 to 12 C atoms, wherein one or more CH2-groups are optionally substituted by one or more non-adjacent CH2-groups are optionally substituted by O, or denotes a radical R P ,

[0882] R P denotes halogen, CN, NCS, R F -, R F -O- or R F -S-, wherein

[0883] R F denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms,

[0884] Z U1 , Z U2 identically or differently, denote -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -C≡C-C≡C- or a single bond, preferably -CF=CF-, -C≡C- or a single bond, very preferably -C≡C- or a single bond,

[0885] X U1 , X U2 identically or differently, denote Cl or F, preferably F,

[0886] and

[0887] denotes a radical selected from the group consisting of

[0888] a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by L,

[0889] b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1 ]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups can be replaced by N, one or more non-adjacent CH2 groups can be replaced by -O- and / or -S- and wherein one or more H atoms can be replaced by L,

[0890] c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, each of which can also be mono- or poly-substituted by L,

[0891] L denotes, on each occurrence, identically or differently, F, Cl, CN, SCN, SF5 or in each case optionally fluorinated linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having from 1 to 12 C atoms, and

[0892] u is 0, 1 or 2, preferably 1,

[0893] wherein the compounds of formula UI are not included in the compounds of formula UII, and wherein the compounds of formula UII and its subformulae are not included in the compounds of formula I, II and III.

[0894] The medium preferably comprises one or more compounds of formula UI and one or more compounds of formula UII.

[0895] Preferably, the compounds of formula UII are selected from the group consisting of formulae UII-1, UII-2 and UII-3, preferably UII-1 and UII-2, in particular UII-1 :

[0896]

[0897] wherein the occurring radicals have the meanings given above for formula UII, and preferably

[0898] and identically or differently denote

[0899]

[0900] X U1 and X U2 denote F, and R U preferably denotes linear or branched or cyclic alkyl or alkenyl having 1 to 7 C atoms, or fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms.

[0901] Very preferred compounds of formula UII are selected from the following subformulae:

[0902]

[0903] wherein R U have the meaning given above and preferably denote linear or branched alkyl having 1 to 7 C atoms, in particular methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0904] The medium according to the application preferably comprises one or more compounds of formulae GF-1-1 to GF-5-1 :

[0905]

[0906]

[0907] wherein R G denote linear or branched alkyl having 1 to 7 C atoms, in particular methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or 2-methylbut-1-yl.

[0908] The medium according to the application comprises one or more chiral dopants. Preferably, the absolute value of the helical twisting power (HTP) of these chiral dopants is in the range of 1 pm -1 to 150 pm -1 , preferably in the range of 10 pm -1 to 100 pm -1 . In case the medium comprises two or more chiral dopants, these can have opposite signs of their HTP values. For some specific embodiments, this condition is preferred because it allows to compensate the chirality of the respective compounds to some extent and thus, can be used to compensate various temperature dependent properties of the resulting medium in the device. Generally, however, it is preferred that the majority of the chiral compounds, preferably all of the chiral compounds present in the medium according to the application have the same sign of their HTP values.

[0909] Preferably, the chiral dopants present in the medium according to the present application are mesogenic compounds and most preferably they exhibit themselves a mesophase.

[0910] In a preferred embodiment of the present application, the medium comprises two or more chiral compounds of algebraic signs having the same HTP.

[0911] The temperature dependence of the HTP of the individual compounds can be high or low. The temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependence of the HTP in the respective ratio.

[0912] For optically active components, the skilled person has a variety of chiral dopants available, some of which are commercially available, such as cholesteryl nonanoate, R- and S-811, R- and S-1011, R- and S-2011, R- and S-3011, R- and S-4011 or CB15 (all from Merck KGaA, Darmstadt).

[0913] Particularly suitable dopants are compounds containing one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups which form mesogenic groups with the chiral groups.

[0914] Suitable chiral groups are, for example, chiral branched hydrocarbon groups, chiral glycols, binaphthols or dioxolanes, furthermore mono- or polyvalent chiral groups selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acid, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or sequences of several, preferably 1 to 5, amino acids.

[0915] Preferred chiral groups are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols, such as, sorbitol, mannitol, iditol, galactitol or a dehydrated derivative thereof, in particular a dianhydrohexitol, such as dianhydrosorbitol (1,4:3,6-dianhydro-D-sorbitol, isosorbide), dianhydromannitol (isosorbitol) or dianhydroiditol (isoiditol); sugar acids, such as, gluconic acid, gulonic acid and ketogulonic acid; chiral substituted diol groups, such as mono- or oligo-ethylene glycol or propylene glycol, wherein one or more CH2groups are substituted by alkyl or alkoxy; amino acids, such as alanine, valine, phenylglycine or phenylalanine or a sequence of 1 to 5 of these amino acids; steroid derivatives, such as a cholesteryl or cholic acid group; terpene derivatives, such as menthyl, neomenthyl, campheyl, pineyl, terpineyl, isolongifolyl, fenchyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.

[0916] The medium according to the application preferably comprises a chiral dopant selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in DE 34 25 503, DE 35 34 777, DE 35 34 778, DE 35 34 779 and DE 35 34 780, DE 43 42 280, EP 01 038 941 and DE 195 41 820. Examples are also the compounds listed in Table F below.

[0917] The chiral compounds preferably used according to the application are selected from the group of the formulae shown below.

[0918] Particularly preferred are chiral dopants selected from the group of the compounds of the following formulae A-I to A-III and A-Ch:

[0919]

[0920] wherein

[0921] R a11 , R a12 and R b12 independently of one another, denote an alkyl group having 1 -15 C atoms, wherein, in addition, one or more non-adjacent CH2groups can each be replaced, independently of one another, by -C(R z ) = C(R z)-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, with O and / or S atoms not being directly connected to one another, and wherein, in addition, one or more H atoms may each be replaced by F, Cl, Br, I or CN, preferably alkyl, more preferably n-alkyl, with the proviso that R a12 With R b12 different

[0922] R a21 and R a22 independently of one another represent an alkyl radical having 1 to 15 C atoms, wherein, in addition, one or more non-adjacent CH2 groups may each independently of one another be replaced by -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- are replaced in such a way that the O and / or S atoms are not directly connected to one another, and wherein, in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN, preferably both are alkyl, more preferably n-alkyl,

[0923] R a31 、R a32 and R b32 independently of one another represent straight-chain and branched alkyl radicals having 1 to 15 C atoms, wherein, in addition, one or more non-adjacent CH2 groups may each independently of one another be replaced by -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- are replaced in such a way that the O and / or S atoms are not directly connected to one another, and wherein, in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN,

[0924] Preferably alkyl, more preferably n-alkyl, provided that R a32 With R b32 different,

[0925] R z represents H, CH3, F, Cl or CN, preferably H or F,

[0926] R 8 With the R given above a11 one of the meanings of , preferably alkyl, more preferably n-alkyl having 1 to 15 C atoms,

[0927] Z 8 represents -C(O)O-, CH2O, CF2O or a single bond, preferably -C(O)O-,

[0928] A 11A is defined as follows 12 or, alternatively, denotes

[0929]

[0930] A 12 denotes

[0931] preferably

[0932]

[0933] wherein

[0934] L 12 independently of one another in each occurrence, halogen, CN or alkyl, alkenyl, alkoxy or alkenyloxy having up to 12 C atoms, and wherein one or more H atoms are optionally replaced by halogen, preferably methyl, ethyl, CI or F, particularly preferably F,

[0935] A 21 denotes

[0936]

[0937] A 22 has the meaning given for A 12

[0938] A 31 has the meaning given for A 11 or, alternatively, denotes A 32 has the meaning given for A 12 n2 is, on each occurrence, identically or differently, 0, 1 or 2, and n3 is 1, 2 or 3, and r is 0, 1, 2, 3 or 4.

[0939] Particularly preferred dopants are compounds selected from the following formulae:

[0940]

[0941]

[0942] wherein

[0943] m is, on each occurrence, identically or differently, an integer from 1 to 9, and

[0944] n is, on each occurrence, identically or differently, an integer from 2 to 9.

[0945] Particularly preferred compounds of formula A are compounds of formula A-III.

[0946] ​Further preferred dopants are derivatives of isosorbide, isomannide or isoidide of the following formula A-IV:

[0947]

[0948] wherein the radicals are

[0949] (dianhydrosorbitol),

[0950] (dianhydromannitol), or

[0951] (dianhydroiditol),

[0952] preferably dianhydrosorbitol,

[0953] and chiral glycols, such as, for example, diphenyl glycol (hydrobenzoin), in particular the mesogenic hydrobenzoin derivatives of the following formula A-V:

[0954]

[0955] including the (S,S) enantiomer, which is not shown,

[0956] wherein

[0957]

[0958] are each, independently of one another, 1,4-phenylene, which can also be mono-, di- or trisubstituted by L, or 1,4-cyclohexylene,

[0959] L is H, F, CI, CN or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms, optionally halogenated,

[0960] c is 0 or 1,

[0961] X is CH2or -C(O)-,

[0962] Z 0 is -COO-, -OCO-, -CH2CH2- or a single bond, and

[0963] R 0 is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy having 1 to 12 carbon atoms.

[0964] Examples of compounds of the formula A-IV are:

[0965]

[0966]

[0967] Compounds of formula A-IV are described in WO 98 / 00428. Compounds of formula A-V are described in GB-A-2,328,207.

[0968] Very particularly preferred dopants are chiral binaphthyl derivatives as described in WO 02 / 94805, chiral binaphthol ketal derivatives as described in WO 02 / 34739, chiral TADDOL derivatives as described in WO 02 / 06265 and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group as described in WO 02 / 06196 and WO 02 / 06195.

[0969] Particularly preferred are chiral compounds of formula A-VI

[0970]

[0971] wherein

[0972] X 1 , X 2 , Y 1 and Y 2 each, independently of one another, F, CI, Br, I, CN, SCN, SF5, straight-chain or branched alkyl having 1 to 25 C atoms which is un- substituted or mono- or poly-substituted by F, CI, Br, I or CN and in which, furthermore, one or more non-adjacent CH2groups can each be replaced, independently of one another, by -O-, -S-, -NH-, NR x -, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- in such a way that O and / or S atoms are not directly linked to one another, a polymerisable group having up to 20 C atoms or a cycloalkyl or aryl group which can optionally be mono- or poly-substituted by halogen, preferably F, or by a polymerisable group,

[0973] x 1 and x 2 each, independently of one another, 0, 1 or 2,

[0974] y 1 and y 2 each, independently of one another, 0, 1, 2, 3 or 4,

[0975] B 1 and B 2are each, independently of one another, aromatic or partially or completely saturated aliphatic six-membered rings, wherein one or more CH groups can each be replaced by an N atom and one or more non-adjacent CH2 groups can each be replaced by O or S,

[0976] W 1 and W 2 are each, independently of one another, -Z 1 -A 1 -(Z 2 -A 2 ) m -R, and one of both is alternatively R 1 or A 3 , but not both are H, or

[0977] is

[0978]

[0979] U 1 and U 2 are each, independently of one another, CH2, O, S, CO or CS,

[0980] V 1 and V 2 are each, independently of one another, (CH2) n wherein one to four non-adjacent CH2 groups can each be replaced by O or S, and V 1 and V 2 are one of both, and in

[0981] is the case,

[0982] both are single bonds,

[0983] n is 1, 2 or 3

[0984] Z 1 and Z 2 are each, independently of one another, -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR x -, -NR x-CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-, -CF2-O-, -O-CF2-, -CF2-S-, -S-CF2-, -CH2-CH2-, -CF2-CH2-, -CH2-CF2-, -CF2-CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, a combination of two of these groups, wherein no two O and / or S and / or N atoms are bound directly to one another, preferably -CH=CH-COO- or -COO-CH=CH- or a single bond,

[0985] R x represents alkyl having 1 to 6 C atoms,

[0986] A 1 , A 2 and A 3 are each, independently of one another, 1,4-phenylene, in which one or two non-adjacent CH groups can each be replaced by N, 1,4-cyclohexylene, in which one or two non-adjacent CH2groups can each be replaced by O or S, 1,3-dioxolan-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidin-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, where each of these groups can be mono- or poly-substituted by L, and furthermore A 1 may be a single bond,

[0987] L is a halogen atom, preferably F, CN, NO2, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 C atoms, where one or more H atoms can each be replaced by F or Cl,

[0988] m is in each case independently 0, 1, 2 or 3, and

[0989] R and R 1 are each, independently of one another, H, F, Cl, Br, I, CN, SCN, SF5, straight-chain or branched alkyl having 1 or 3 to 25 C atoms, which can optionally be mono- or poly-substituted by F, Cl, Br, I or CN and in which one or more non-adjacent CH2groups can each be replaced by -O-, -S-, -NH-, -NR 0 -, -CO-, -COO-, -OCO-, -O-COO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C-, where no two O and / or S atoms are bound directly to one another, or a polymerisable group.

[0990] Particularly preferred are chiral binaphthyl derivatives of formula A-VI-1

[0991]

[0992] wherein ring B, R 0 and Z 0 as defined for formula A-IV and A-V, and b is 0, 1, or 2,

[0993] In particular those selected from the following formulae A-VI-1a to A-VI-1c:

[0994]

[0995] wherein ring B, R 0 , and Z 0 as defined for formula A-VI-1, and

[0996] R 0 as defined for formula A-IV, or H or alkyl having 1 to 4 carbon atoms, and

[0997] b is 0, 1 or 2,

[0998] and Z 0 is in particular -OC(O)- or a single bond.

[0999] The concentration of the one or more chiral dopants in the LC medium is preferably in the range of from 0.001 % to 20 %, preferably from 0.05 % to 5 %, more preferably from 0.1 % to 2 %, and most preferably from 0.5 % to 1.5 %. These preferred concentration ranges are particularly suitable for the chiral dopants S-4011 or R-4011 (both from Merck KGaA) and chiral dopants having the same or similar HTP. For chiral dopants having a higher or lower absolute value of the HTP compared to S-4011, these preferred concentrations have to be decreased proportionally to their HTP value relative to S-4011, or increased proportionally.

[1000] The pitch p of the LC medium or host mixture according to the present application is preferably in the range of from 5 to 50 pm, more preferably from 8 to 30 pm and particularly preferably from 10 to 20 pm.

[1001] Preferably, the medium according to the present application comprises a stabilizer selected from the compounds of formulae ST-1 to ST-22.

[1002]

[1003]

[1004]

[1005]

[1006]

[1007] wherein

[1008] R ST represents H, alkyl or alkoxy having 1 to 15 C atoms, wherein, in addition, one or more CH2groups in these radicals can each be replaced, independently of one another, by -C≡C-, -CF2O-, -OCF2-, -CH=CH-, -O-, -CO-O-, -O-CO-, in such a way that the O atoms are not directly linked to one another, and wherein, in addition, one or more H atoms can be replaced by halogen,

[1009] represents

[1010]

[1011]

[1012] Z ST each, independently of one another, represents -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)4-, -CH=CH-CH2O-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C- or a single bond,

[1013] L 1 and L 2 each, independently of one another, represents F, Cl, CF3or CHF2,

[1014] n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7,

[1015] n2is on each occurrence, identically or differently, preferably identically, an integer from 1 to 12, preferably 2, 3, 4, 5 or 6, very preferably 3, and

[1016] R S on each occurrence, identically or differently, preferably identically, represents alkyl having 1 to 6 C atoms, preferably n-butyl,

[1017] p represents 1 or 2, and

[1018] q represents 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[1019] Particularly preferred among the compounds of formula ST are compounds of the formula

[1020]

[1021] wherein n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 1 or 7

[1022]

[1023] wherein n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 3

[1024]

[1025] wherein n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 3

[1026]

[1027]

[1028] In the compounds of formula ST-3a and ST-3b, n preferably denotes 3. In the compounds of formula ST-2a, n preferably denotes 7.

[1029] Very particularly preferred mixtures according to the application comprise one or more stabilizers from the group of compounds of formulae ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1 and ST-12:

[1030]

[1031]

[1032] The compounds of formulae ST-1 to ST-12 are preferably each present in the liquid-crystalline mixture according to the application in an amount of 0.005 to 0.5%, very preferably in an amount of 100 ppm, 250 ppm, 500 ppm or 1000 ppm, based on the mixture.

[1033] If the mixture according to the application comprises two or more compounds selected from the group of compounds of formulae ST-1 to ST-18, the concentration is increased to 0.01 to 1 %, based on the mixture, in the case of two mixtures.

[1034] The total proportion of compounds of formulae ST-1 to ST-18, however, should not exceed 2%, based on the mixture according to the application.

[1035] Other mesogenic compounds not explicitly mentioned above can optionally and advantageously also be used in the media according to the application. Such compounds are known to the person skilled in the art.

[1036] In a preferred embodiment of the present application, the media comprise one or more compounds of formula D in a total concentration of 1 to 20 %, more preferably 5 to 15 %, and particularly preferably 8 to 12 %.

[1037] In a preferred embodiment of the present application, the liquid-crystalline media comprise compounds of formula T in a total concentration preferably in the range of 5 to 35 %, more preferably 6 to 30 %, and particularly preferably 7 to 25 %, which compounds of formula T are preferably selected from formulae T-1 a, T-2a and T-3a, very preferably from T-1 a-5, T-2a-2, T-2a-4 and T-3a-2.

[1038] In a preferred embodiment, the media comprise one or more compounds of formula I, preferably of formulae I-2 or I-3, in a total concentration in the range of 1 to 30 %, more preferably 2 to 25 %, very preferably 3 to 20 % and particularly preferably 5 to 15 %.

[1039] In a preferred embodiment of the present application, the media comprise one or more compounds selected from compounds of formulae II and GF-1-3 and UI-1-3, preferably of formulae II-1 and / or UI-1-3, in a total concentration of 2 to 35 %, more preferably 3 to 30 %, and particularly preferably 5 to 25 %.

[1040] In a preferred embodiment of the present application, the media comprise one or more compounds of formula IIA-1 in a total concentration of 5 to 25 %, more preferably 8 to 20 %, and particularly preferably 12 to 17 %.

[1041] In a preferred embodiment of the present application, the media comprise one or more compounds of formula II-1 in a total concentration of 30 % or less, more preferably 25 % or less, and particularly preferably 22 % or less.

[1042] In a preferred embodiment of the present application, the media comprise one or more compounds selected from formulae III and Ilia-1 to Ilia-4, preferably III-1 and / or III-2 and / or Ilia-2 and / or Ilia-3, more preferably III-1 f and / or III-1 b, and / or III-1 h and / or Ilia-2, in a total concentration of 15 to 60 % or 65 % or 70 %, more preferably 20 to 58 %, and particularly preferably 30 to 55 % or 35 to 53 %.

[1043] In a preferred embodiment of the present application, the medium comprises one or more compounds of formula XII, preferably in a total concentration of 5 to 30 %, more preferably 8 to 25 %, and particularly preferably 10 to 20 %.

[1044] In a preferred embodiment, the medium comprises one or more compounds of formula D and one or more compounds selected from the group consisting of formulae I, II and / or IIA, III, XII, T, preferably in a total concentration of 90 % or more, more preferably 95 %, 96 % or 97 % or more, very preferably 98 % or more and particularly preferably 99 % or more.

[1045] In a preferred embodiment, the medium comprises one or more compounds of formula D and one or more compounds selected from the group consisting of formulae I, II and / or IIA, III, XII, T, in a total concentration in the range of 40 to 90 %; and one or more compounds of formula IV in a total concentration of 10 % or more.

[1046] In a preferred embodiment, the medium comprises one or more compounds of formula D and one or more compounds selected from the group consisting of formulae I, II and / or IIA, III, XII, T, in a total concentration in the range of 40 to 70 %; and one or more compounds of formula IV in a total concentration of 30 % or more.

[1047] In a preferred embodiment, the medium comprises one or more compounds of formula D and one or more compounds selected from the group consisting of formulae I, II and / or IIA, III, XII, T, in a total concentration in the range of 40 to 60 %; and one or more compounds of formula IV in a total concentration of 40 % or more.

[1048] Further preferred embodiments of the present application, alone or in combination with each other, are shown below, wherein some compounds are abbreviated using the acronyms described in Tables A and B, and given in Table C below, n is 1, 2, 3, 4, 5, 6 or 7:

[1049] - the medium comprises one or more compounds of formula XII-3, preferably compounds of formula CPU(F.F)-n-S, preferably in a concentration in the range of 10 to 30 %, in particular 15 to 25 %;

[1050] - the medium comprises one, two, three, four or more compounds of formula III-1, preferably compounds selected from formulae III-1 b, III-1 f and III-1 h; more preferably compounds of III-1 b and III-1 h;

[1051] - the medium comprises compounds of formula III-1 b, preferably in a total concentration in the range of 5 to 40 %, more preferably 10 to 35 %, in particular 15 to 30 %.

[1052] - the medium comprises the compounds of formula III-1 h in a total concentration in the range of 7 % to 35 %, more preferably 10 % to 30 %, in particular 12 % to 25 %;

[1053] - the medium comprises the compounds PPU-TO-S and / or PPTU-TO-S and / or PTPU-TO-S and / or PP(1)TO-n-S;

[1054] - the medium comprises one or more compounds of formula I-2d, preferably the compounds PGU-2-S and / or PGU-3-S and / or PGU-4-S, and / or CPU-2-S and / or CPU-3-S and / or CPU-4-S;

[1055] - the medium comprises one or more compounds of formula II-1 b, preferably the compounds PTU-4-S and / or PTU-5-S;

[1056] - the medium comprises one or more compounds of formula PPTU-n-S and / or PTPU-n-S in a total concentration in the range of 15 % to 25 %;

[1057] - the medium comprises one or more compounds of formula PPTU-n-S and / or PTPU-n-S and / or PGTU-n-S in a total concentration in the range of 15 to 30 %, wherein n is 1, 2, 3, 4, 5 or 6;

[1058] - the medium comprises one or more compounds of formula CPTU-n-S in a total concentration in the range of 10 % to 30 %, in particular 14 % to 25 %;

[1059] - the medium comprises one or more compounds of formula ST-3, preferably ST-3a and / or ST-3b, in particular ST-3b-1, in a total concentration in the range of 0.01 to 0.1 %, preferably 0.05 to 0.5 %, in particular 0.10 to 0.15 %.

[1060] The liquid-crystalline medium according to the present application preferably has a clearing point of 90 °C or more, more preferably 100 °C or more, more preferably 1 10 °C or more, more preferably 120 °C or more, more preferably 130 °C or more, particularly preferably 140 °C or more and very particularly preferably 150 °C or more.

[1061] The nematic phase of the medium according to the present application preferably extends at least from 0°C or below to 90°C or above. Advantageously, the medium according to the present application exhibits an even broader nematic phase range, preferably at least -10°C or below to 120°C or above, very preferably at least -20°C or below to 140°C or above, and in particular -30°C or below to 150°C or above, very particularly preferably at least -40°C or below to 170°C or above.

[1062] The liquid-crystalline medium according to the present application preferably has a Δε of 5 or more, more preferably of 7 or more, and very preferably of 8 or more at 1 kHz and 20°C.

[1063] The liquid-crystalline medium according to the present application preferably has a birefringence (Δn) of 0.280 or more, more preferably of 0.300 or more, even more preferably of 0.320 or more, very preferably of 0.330 or more, and in particular of 0.350 or more at 589 nm (Na D ) and 20°C.

[1064] The liquid-crystalline medium according to the present application preferably has a Δn in the range of 0.200 to 0.900, more preferably in the range of 0.250 to 0.800, even more preferably in the range of 0.300 to 0.700, and very particularly preferably in the range of 0.350 to 0.600 at 589 nm (Na D ) and 20°C.

[1065] In a preferred embodiment of the present application, the Δn of the liquid-crystalline medium according to the present application is preferably 0.50 or more, more preferably 0.55 or more.

[1066] The compounds of the formulae I to III comprise in each case dielectrically positive compounds having a dielectric anisotropy of greater than 3, dielectrically neutral compounds having a dielectric anisotropy of less than 3 and greater than -1.5, and dielectrically negative compounds having a dielectric anisotropy of -1.5 or less.

[1067] The compounds of the formulae D, I, II and III are preferably dielectrically positive.

[1068] Preferably, the optical assembly according to the present application is designed and configured as an optical phase modulator.

[1069] In a preferred embodiment, the optical assembly according to the present application is designed and configured for use in a transmissive device for phase modulation of IR radiation.

[1070] In another preferred embodiment, the optical assembly according to the present application is designed and configured for use in a reflective device for phase modulation of IR radiation.

[1071] A typical electro-optical modulator comprises electrically conductive infrared transmissive windows, e.g. consisting of Ge, separated from each other by spacers and having a cell gap in the range of 1 mm to 5 mm.

[1072] According to another aspect of the present application, there is provided a LIDAR scanning system as described in WO 2018 / 156643 Al, comprising a laser configured to emit pulses of light at an operating wavelength in the infrared. The LIDAR scanning system comprises a transmissive reconfigurable metasurface configured to reflect incoming pulses of light from the laser as an illumination beam directed at a selected portion of a field of view, preferably a two-dimensional field of view. The direction of the illumination beam is responsive to a first selected holographic beam steering pattern implemented in the transmissive reconfigurable metasurface. The system further comprises a receiving reconfigurable metasurface configured to reflect returns of the illumination beam from the selected portion of the field of view as a relay beam directed at an optical detector. The direction of the relay beam is responsive to a second selected holographic beam steering pattern implemented in the receiving reconfigurable metasurface. The system comprises an optical detector comprising an array of detector pixels. Each detector pixel comprises (i) a light detector configured to detect light in the returns of the illumination beam; and (ii) a timing circuit configured to determine a time of flight of the detected light. The optical detector is further configured to output a detection signal indicative of the detected light and the time of flight of the detected light for each pixel of the array. The transmissive reconfigurable metasurface comprises a plurality of dynamically tunable high-Q dielectric resonators arranged on a surface of the reconfigurable metasurface, the surface having a sub-wavelength pitch smaller than the operating wavelength of the laser, wherein the surface of the reconfigurable metasurface comprises an electrically conductive surface and the plurality of resonators have a corresponding plurality of tunable reflection phases that provide a dynamically tunable reflected wave responsive to an incident wave, wherein the electrically conductive surface and the plurality of resonators define a metasurface. Each of the plurality of dielectric resonators comprises (i) a pair of regions having a higher refractive index; and (ii) an electrically tunable material disposed in a gap between the regions, wherein the electrically tunable material is a liquid crystal material as set forth above and below.

[1073] According to another aspect of the present application, there is provided a reflective spatial light modulator, in particular a LCoS device, comprising a liquid crystal material according to the present application sandwiched between a transparent glass layer having transparent electrodes, a mirror surface mounted on a silicon CMOS substrate and a PCB. The mirror surface is divided into a two-dimensional array of individually addressable pixels. Each pixel can be individually driven by a voltage signal to provide a local phase change to at least one polarization component of an optical signal, thereby providing a two-dimensional array of phase steering regions. The pre-alignment of the liquid crystal is provided by an alignment layer.

[1074] The LCoS device is suitable for integration into optical devices. Preferred devices are wavelength selective switches (WSS), LIDAR scanners, infrared scene projectors and other beam steering applications as shown in the following paper by Micallef, F. (2019) Middle infrared beam-steering using liquid crystals for spatial light modulation (Doctoral thesis). https: / / doi.org / 10.17863 / CAM.39602 (https: / / www.repository.cam.ac.uk / handle / 1810 / 292443).

[1075] In this application, the expression dielectric positive describes compounds or components where Δε > 3.0, dielectric neutral those where -1.5 < Δε < 3.0, and dielectric negative those where Δε < -1.5. Δε is measured at a frequency of 1 kHz and at 20 °C. The dielectric anisotropy of each compound is determined from a 10% solution of each individual compound in a nematic host mixture. If the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitance of the test mixture is measured in both a cell with homeotropic alignment and a cell with planar alignment. The cell gap for both types of cell is about 20 μm. The applied voltage is a square wave with a frequency of 1 kHz and a root mean square value of typically 0.5 to 1.0 V, but it is always chosen to be below the threshold of the capacitance of each test mixture.

[1076] Δε is defined as (ε || - ε ⊥ ) and ε ave is (ε || + 2ε ⊥ ) / 3.

[1077] The host mixture used for the determination of physical constants of pure compounds by extrapolation is ZLI-4792 from Merck KGaA, Germany. The absolute value of the dielectric constant, the birefringence (Δn) and the rotational viscosity (γ1) of the compounds are determined from the change of the respective values of the host mixture after addition of the compounds. The concentration in the host is 10%, or 5% in case of insufficient solubility. The values are extrapolated to a 100% concentration of the added compounds.

[1078] In the examples, the following abbreviations are used to give the phase sequence of the pure compounds:

[1079] K: crystalline, N: nematic, SmA: smectic A, SmB: smectic B, I: isotropic.

[1080] The components having a nematic phase are measured as such at a measurement temperature of 20°C, all other component treatments being analogous.

[1081] In both cases, the expression "threshold voltage" in this application means the optical threshold and is given for a relative contrast of 10% (V 10 ) and the expression "saturation voltage" means the optical saturation and is given for a relative contrast of 90% (V 90 ). The capacitive threshold voltage (V0), also called Freedericks threshold, is used only when explicitly mentioned. Fr

[1082] The parameter ranges indicated in this application include the limit values, unless explicitly stated otherwise.

[1083] The different upper and lower values indicated for different property ranges are combined with each other to give further preferred ranges.

[1084] Throughout the application the following conditions and definitions apply, unless stated otherwise. All concentrations are given in percent by weight and relate to the respective overall mixture, all temperature values are given in degrees Celsius and all temperature differences in differential degrees. All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA (Germany) and are given for a temperature of 20°C, unless explicitly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltage and all other electro-optical properties are determined using test cells produced by Merck KGaA, Germany. The cell thickness of the test cells used to determine Δε is approximately 20 μm. The electrodes are circular ITO electrodes with an area of 1.13 cm 2 and a guard ring for homeotropic alignment (e || ) and polyimide AL-1054 from Japan Synthetic Rubber for planar alignment (e ⊥ ). The Solatron 1260 frequency response analyzer is used with a sinusoidal wave and a voltage amplitude of 0.3 V rms ​capacitance. The light used in the electro-optical measurement is white light. The setup used here is a commercial DMS instrument from Autronic-Melchers, Germany. The characteristic voltages are determined under normal observation. The threshold voltage (V 10 ), the middle gray voltage (V 50 ) and the saturation voltage (V 90 ) are determined for 10%, 50% and 90% relative contrast, respectively.

[1085] Liquid crystal media are investigated in the microwave frequency range with respect to their properties as described in A. Penirschke et al. "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz", 34 th European Microwave Conference - Amsterdam, pp. 545-548. In this respect also A. Gaebler et al. "Direct Simulation of Material Permittivities... ", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467 and DE 10 2004 029 429 A are compared, where the measurement method is also described in detail.

[1086] The liquid crystal is introduced into a polytetrafluoroethylene (PTFE) or quartz capillary. The inner diameter of the capillary is 0.5 mm and the outer diameter is 0.78 mm. The effective length is 2.0 cm. The filled capillary is introduced into the center of a cylindrical cavity with a resonance frequency of 19 GHz. The length of the cavity is 11.5 mm and the radius is 6 mm. Then an input signal (source) is applied and the frequency-dependent response of the cavity is recorded using a commercial vector network analyzer (N5227A PNA microwave network analyzer, Keysight Technologies Inc. USA). For other frequencies the dimensions of the cavity are adapted accordingly.

[1087] The change in resonance frequency and Q-factor between the measurement with a capillary filled with liquid crystal and the measurement without a capillary filled with liquid crystal is used to determine the dielectric constant and the loss angle at the respective target frequency, which is described in the above publication A. Penirschke et al., 34 thThe values of the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by the alignment of the liquid crystal in a magnetic field. For this purpose, the magnetic field of a permanent magnet is used. The magnetic field strength is 0.35 Tesla.

[1088] The values of the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by the alignment of the liquid crystal in a magnetic field. For this purpose, the magnetic field of a permanent magnet is used. The magnetic field strength is 0.35 Tesla.

[1089] Preferred components are phase shifters, varactor diodes, wireless and radio wave antenna arrays, matching circuits, adaptive filters and others.

[1090] In the present application, the term "compound" means one compound as well as a plurality of compounds, unless explicitly stated otherwise.

[1091] All mixtures according to the present application are nematic. The liquid-crystalline medium according to the present application preferably has a nematic phase in the preferred ranges given above. The expression having a nematic phase here means on the one hand that no smectic phase is observed at low temperature and no crystallization is observed at the respective temperature, on the other hand that no clearing occurs upon heating from the nematic phase. The clearing point is measured at high temperature by the conventional method in a capillary. The investigation at low temperature is carried out in a flow viscosimeter at the respective temperature and checked by storage of bulk samples: The storage stability (LTS) in the bulk of the medium according to the present application at a given temperature T is determined by visual inspection. 2 g of the medium of interest are filled into a closed glass container (bottle) of suitable size which is placed in a refrigerator at the predetermined temperature. The bottles are checked at defined time intervals for the occurrence of a smectic phase or crystallization. For each material and each temperature, two bottles are stored. If the occurrence of a crystallization or a smectic phase is observed in at least one of the two respective bottles, the test is terminated and the time of the last check before the occurrence of the higher ordered phase is observed is noted as the respective storage stability. The test is finally terminated after 1000 hours, i.e. an LTS value of 1000 hours means that the mixture is stable at the given temperature for at least 1000 hours.

[1092] The liquid crystals employed preferably have a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more and very particularly preferably 10 or more.

[1093] Furthermore, the liquid-crystalline media according to the present application are characterized by high anisotropy values in the microwave range. The birefringence at about 19 GHz is for example preferably 0.14 or more, particularly preferably 0.15 or more, particularly preferably 0.20 or more, particularly preferably 0.25 or more and very particularly preferably 0.30 or more. In addition, the birefringence is preferably 0.80 or less.

[1094] The dielectric anisotropy in the microwave range is defined as

[1095] Δε r ≡(ε r, ||-ε r, ⊥).

[1096] The tunability (τ) is defined as

[1097] τ≡(Δε r / ε r, ||).

[1098] The material quality (η) is defined as

[1099] η≡(τ / tanδ εr,max. ), wherein

[1100] The maximum dielectric loss is

[1101] tanδ εr,max ≡max.{tanδ εr,⊥ , tanδ εr,||}.

[1102] The tunability τ of the medium according to the application measured at 20°C and 19 GHz is 0.250 or more, preferably 0.300 or more, 0.310 or more, 0.320 or more, 0.330 or more, or 0.340 or more, very preferably 0.345 or more and in particular 0.350 or more.

[1103] The material quality (η) of the preferred liquid crystal material is 6 or more, preferably 8 or more, preferably 10 or more, preferably 15 or more, preferably 17 or more, preferably 20 or more, particularly preferably 25 or more and very particularly preferably 30 or more.

[1104] The phase shifter quality of the preferred liquid crystal material in the respective component is 15° / dB or more, preferably 20° / dB or more, preferably 30° / dB or more, preferably 40° / dB or more, preferably 50° / dB or more, particularly preferably 80° / dB or more and very particularly preferably 100° / dB or more.

[1105] However, in some embodiments it can also be advantageous to use liquid crystals having a negative value of the dielectric anisotropy.

[1106] The liquid crystals used are either single substances or mixtures. They preferably have a nematic phase.

[1107] The liquid-crystalline media according to the invention may contain other additives and chiral dopants in customary concentrations. The total concentration of these other components, based on the entire mixture, is 0% to 10%, preferably 0.1% to 6%. The concentration of the individual compounds used is preferably 0.1% to 3%. The concentrations of these and similar additives are not taken into account when quoting values ​​and concentration ranges for the liquid-crystalline components and liquid-crystalline compounds of the liquid-crystalline media in this application.

[1108] Preferably, the media according to the invention contain one or more chiral compounds as chiral dopants to adjust their cholesteric pitch. Their total concentration in the media according to the invention is preferably in the range of 0.05% to 15%, more preferably 1% to 10% and most preferably 2% to 6%.

[1109] Optionally, the media according to the invention may contain other liquid crystal compounds to adjust the physical properties. Such compounds are known to those skilled in the art. Their concentration in the media according to the invention is preferably 0% to 30%, more preferably 0.1% to 20%, and most preferably 1% to 15%.

[1110] For relative tuning or relative contrast ratio of photoelectric response, respectively, the relative contrast ratio is varied from 0% to 90% (t 90 -t0), the response time is based on the rise time (τ on ) is given, including the delay time (t 10 -t0); for relative tuning or relative contrast of photoelectric response changes from 100% back to 10% (t 100 -t 10 ) time, the response time is the decay time (τ off ) is given, and the total response time (τ 总计 =τ on +τ off ).

[1111] The liquid crystal medium according to the present invention is composed of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20, and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. Typically, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. The completion of the dissolution process is particularly easily observed if the temperature is above the clearing point of the compound used in the higher concentration. However, the medium can also be prepared in other conventional ways, such as using so-called premixes, which can, for example, be a homogeneous mixture or eutectic mixture of the compounds, or using so-called "multi-bottle" systems, whose components themselves are ready-to-use mixtures.

[1112] All temperatures, such as melting point T(C,N) or T(C,S), transition from smectic (S) phase to nematic (N) phase T(S,N) and clearing point T(N,I) of the liquid crystal, are indicated in degrees Celsius. All temperature differences are indicated in degrees difference.

[1113] In the present application and in particular in the following examples, the structure of the mesogenic compounds is indicated by means of abbreviations (also called acronyms). In these acronyms, the chemical formula is abbreviated using the following Tables A to C. All groups C n H 2n+1 , C m H 2m+1 and C l H 2l+1 and C n H 2n-1 , C m H 2m-1 and C l H 2l-1 denote straight-chain alkyl or alkylene groups, respectively, having n, m or I C atoms in each case, wherein n and m are independently 1, 2, 3, 4, 5, 6 or 7, and I is 1, 2 or 3. Table A lists the codes for the ring elements of the core structure of the compounds, while Table B shows the linking groups and end groups. Table C shows illustrative structures of the compounds and their respective abbreviations.

[1114] Table A: Ring elements

[1115]

[1116]

[1117]

[1118]

[1119]

[1120] Table B: Linking groups

[1121]

[1122]

[1123] Table B: End groups

[1124]

[1125] Used in combination with other

[1126]

[1127] where n and m each represent an integer, and the three dots "..." is a placeholder for other abbreviations from this table.

[1128] Branching side groups are numbered from the position next to the longest chain of rings (1), with the smaller number indicating the length of the branch, and the superscript number in parentheses indicating the position of the branch, e.g.:

[1129]

[1130] The following table shows illustrative structures and their corresponding abbreviations. These are shown to illustrate the meaning of the abbreviation rules. They also represent preferred compounds for use in the medium.

[1131] Table C: Illustrative structures

[1132] The following illustrative structures are examples and compounds, which are additionally preferred for use in the medium:

[1133]

[1134]

[1135]

[1136]

[1137]

[1138]

[1139]

[1140]

[1141]

[1142]

[1143]

[1144]

[1145]

[1146]

[1147]

[1148]

[1149]

[1150]

[1151] wherein m and n are, identically or differently, 1, 2, 3, 4, 5, 6 or 7.

[1152] Preferably, the medium according to the present application comprises one or more compounds selected from the group of compounds of Table C.

[1153] The following table, Table D, shows illustrative compounds which can be used as alternative stabilizers in the mesogenic medium according to the present application. The total concentration of these and similar compounds in the medium is preferably 5% or less.

[1154] Table D

[1155]

[1156]

[1157]

[1158] In a preferred embodiment of the present application, the mesogenic medium comprises one or more compounds selected from the group of compounds from Table D.

[1159] The following table, Table E, shows illustrative compounds which can be used as chiral dopants, preferably in the mesogenic medium according to the present application.

[1160] Table E

[1161]

[1162]

[1163]

[1164] In a preferred embodiment of the present application, the mesogenic medium comprises one or more compounds selected from the group of compounds from Table E.

[1165] The mesogenic medium according to the present application preferably comprises two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.

[1166] Parts or percentage data represent parts by weight or percent by weight, unless otherwise indicated.

[1167] In the foregoing and hereinafter:

[1168] V o Vthrepresents the threshold voltage at 20°C, capacitive [V]

[1169] n eIndicates the extraordinary refractive index at 20°C and 589nm.

[1170] n o It represents the ordinary refractive index at 20°C and 589nm.

[1171] Δn represents the optical anisotropy at 20°C and 589 nm.

[1172] ε ⊥ represents the dielectric permittivity perpendicular to the director at 20°C and 1kHz,

[1173] ε || represents the dielectric permittivity parallel to the director at 20°C and 1kHz,

[1174] Δε represents the dielectric anisotropy at 20°C and 1kHz,

[1175] clp., T(N,I) represents the clearing point [℃],

[1176] γ1 represents the rotational viscosity [mPa·s] measured at 20°C,

[1177] K1 represents the elastic constant at 20°C, the “bending” deformation [pN],

[1178] K2 represents the elastic constant at 20°C, "torsion" deformation [pN],

[1179] K3 represents the elastic constant at 20°C, "bending" deformation [pN],

[1180] K avg. represents the average elastic constant, which is defined as and

[1181] LTS stands for low temperature stability (nematic phase) determined as detailed in test cells or in bulk.

[1182] Unless otherwise expressly stated, all values ​​in this application regarding temperature (such as melting point T(C,N), transition from smectic (S) phase to nematic (N) phase T(S,N), and clearing point T(N,I) or clp.) are indicated in degrees Celsius (°C). Mp represents the melting point. Furthermore, Tg = glassy state, C = crystalline state, N = nematic phase, S = smectic phase, and I = isotropic phase. The numbers between these symbols represent the transition temperatures.

[1183] Unless otherwise expressly indicated, the term "threshold voltage" as used in the present invention relates to the capacitance threshold (V0), also known as the Freedericksz threshold. In embodiments, as is generally common, the optical threshold (V 10 ).

[1184] The display for measuring the capacitive threshold voltage consists of two plan-parallel glass outer plates with a spacing of 20 pm, each having an electrode layer on the inner side and on top an unrubbed polyimide alignment layer, which enables a homeotropic edge alignment of the liquid crystal molecules.

[1185] By so-called "HTP" is meant the helical twisting power (in pm) of an optically active or chiral substance in an LC medium. HTP is measured on the commercially available nematic LC host mixture MLD-6260 (Merck KGaA) at a temperature of 20 °C, unless indicated otherwise.

[1186] Clearing point is measured using a Mettler Thermosystem FP900. Optical anisotropy (An) is measured using an Abbe Refractometer H005 (sodium spectral lamp Na 10 at 589 nm, 20 °C). Dielectric anisotropy (De) is measured using an LCR-Meter E4980A / Agilent (G005) with an e-parallel cell of JALS2096-R1 at 20 °C. Switching voltage (Vo) is measured using an LCR-Meter E4980A / Agilent (G005) with an e-parallel cell of JALS2096-R1 at 20 °C. Rotational viscosity (Y1) is measured using a TOYO LCM-2 (0002) with a Y1 minus cell of JALS-2096-R 1 at 20 °C. Elastic constant (K1, splay) is measured using an LCR-Meter E4980A / Agilent (G005) with an e-parallel cell of JALS2096-R1 at 20 °C. K3: Elastic constant (K3, bend) is measured using an LCR-Meter E4980A / Agilent (G005) with an e-parallel cell of JALS2096-R1 at 20 °C.

[1187] All concentrations in this application are indicated in percent by weight, and relate to the respective mixture as a whole (without solvents) comprising all solid or liquid crystal components, unless explicitly indicated otherwise. All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA, Germany, and apply to a temperature of 20 °C, unless explicitly indicated otherwise. Examples

[1188] The application is illustrated in detail by the following non-limiting working examples.

[1189] Synthesis Examples

[1190] The following abbreviations are used:

[1191] RT room temperature

[1192] MTB ether tert-butyl methyl ether

[1193] DABCO 1,4-diazabicyclo[2.2.2]octane

[1194] dist. distillation

[1195] RP reversed phase

[1196] THF tetrahydrofuran

[1197] XPhos 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

[1198] XPhos Pd G2 chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'- biphenyl)[2-(2'-amino-1,1'-biphenyl)palladium(II)

[1199] Synthesis Example 1: 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3- pentyl-1,2-dihydronaphthalene

[1200] Step 1.1: 7-bromo-3-pentyl-1,2-dihydronaphthalene

[1201]

[1202] A solution of 6-bromo-3,4-dihydronaphthalen-2-yl trifluoromethanesulfonate (CAS 1013891-56-9) (12.0 g, 34 mmol) in THF (150 ml) was treated with cobalt(III) acetylacetonate (360 mg, 1.01 mmol) at -20 °C under an argon atmosphere. Pentylmagnesium bromide (25 ml of a 2M solution in diethyl ether) was added dropwise at -20 °C and the reaction mixture was stirred at -20 °C for 2 hours. It was then quenched with ice water (100 ml), acidified with hydrochloric acid (2N) and extracted twice with MTB ether. The combined organic phases were dried (sodium sulfate), filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane) followed by RP chromatography (eluent acetonitrile) to give 7-bromo-3-pentyl-1,2-dihydronaphthalene as a colourless oil.

[1203] Step 1.2: 2,6-difluoro-4-((6-pentyl-7,8-dihydronaphthalen-2-yl)ethynyl)aniline

[1204]

[1205] A solution of 7-bromo-3-pentyl-1,2-dihydronaphthalene (3.2 g, 11 mmol) and 4- ethynyl-2,6-difluoroaniline (CAS 753501 -37-0) (1.9 g, 12 mmol) in THF (25 ml) and diisopropylamine (25 ml) was treated with XPhos (1 1 mg, 0.02 mmol), XPhos Pd G2 (18 mg, 0.02 mmol) and copper(I) iodide (2.2 mg, 0.01 mmol) at 50 °C under an argon atmosphere and the reaction mixture was stirred at reflux temperature for 4 h. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and extracted with MTB ether and the combined organic phases were washed with brine and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) to give 2,6-difluoro-4-((6-pentyl-7,8-dihydronaphthalen-2-yl)ethynyl)aniline as a colourless solid.

[1206] Step 1.3: 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3-pentyl-1,2- dihydro naphthalene

[1207]

[1208] Thionyl chloride (0.9 ml, 1 1 mmol) was slowly added to a solution of 2,6-difluoro-4-((6-pentyl-7,8-dihydronaphthalen-2-yl)ethynyl)aniline (3.0 g, 9 mmol) and DABCO (3.0 g, 27 mmol) in dichloromethane (50 ml) at 0 °C under an argon atmosphere and the reaction mixture was stirred at room temperature for 1 h. It was then quenched with distilled water (1 ml), filtered over silica gel, washed with dichloromethane and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) and subsequent crystallization (heptane and heptane / acetone) to give 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3-pentyl-1,2-dihydronaphthalene as yellowish crystals.

[1209] Phase sequence: K 75 N 84 I

[1210] Δn = 0.4218

[1211] Δε = 20.4

[1212] Synthesis Example 2: 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3-(pent-1 -yn-1 -yl)- 1,2-dihydronaphthalene

[1213] Step 2.1 : 7-bromo-3-(pent-1 -yn-1 -yl)-1,2-dihydronaphthalene

[1214]

[1215] A solution of 6-bromo-3,4-dihydronaphthalen-2-yl trifluoromethanesulfonate (CAS 1013891-56-9) (9.5 g, 27 mmol) and pent-1-yn (1.9 g, 28 mmol) in THF (60 ml) and triethylamine (30 ml) was treated with bis(triphenylphosphine)palladium(II) chloride (187 mg, 0.3 mmol) and copper(I) iodide (56 mg, 0.3 mmol) under an argon atmosphere and the reaction mixture was stirred at 40 °C for 2 hours. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and extracted with MTB ether and the combined organic phases were washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane) followed by RP chromatography (eluent acetonitrile) to give 7-bromo-3-(pent-1-yn-1-yl)-1,2-dihydronaphthalene as a yellow oil.

[1216] Step 2.2: 2,6-difluoro-4-((6-(pent-1-yn-1-yl)-7,8-dihydronaphthalen-2-yl)ethynyl)aniline

[1217]

[1218] To a solution of 7-bromo-3-(pent-1-yn-1-yl)-1,2-dihydronaphthalene (5.6 g, 20 mmol) and 4-ethynyl-2,6-difluoroaniline (CAS 753501-37-0) (3.1 g, 20 mmol) in THF (45 ml) and diisopropylamine (45 ml) was added XPhos (19 mg, 0.04 mmol), XPhos Pd G2 (32 mg, 0.04 mmol) and copper(I) iodide (3.8 mg, 0.02 mmol) at 50 °C under an argon atmosphere and the reaction mixture was stirred at reflux temperature for 4 hours. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and extracted with MTB ether and the combined organic phases were washed with brine and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) to give 2,6-difluoro-4-((6-(pent-1-yn-1-yl)-7,8-dihydronaphthalen-2-yl)ethynyl)aniline as a colourless solid.

[1219] Step 2.3: 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3-(pent-1-yn-1-yl)-1,2- dihydronaphthalene

[1220]

[1221] Thionyl chloride (1.8 ml, 23 mmol) was slowly added to a solution of 2,6-difluoro-4-((6-(pent-1-yn-1-yl)-7,8-dihydronaphthalen-2-yl)ethynyl)aniline (5.8 g, 17 mmol) and DABCO (5.0 g, 45 mmol) in dichloromethane (80 ml) at 0 °C under an argon atmosphere and the reaction mixture was stirred at room temperature overnight. It was then quenched with distilled water (2 ml), filtered over silica gel, washed with dichloromethane and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) and subsequent crystallization (heptane / acetone) to yield 7-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-3-(pent-1-yn-1-yl)-1,2-dihydronaphthalene as yellow crystals.

[1222] Phase sequence: K 89 N (80) I

[1223] Δn = 0.5352

[1224] Δε = 20.7

[1225] Synthesis Example 3: 7-(3,5-difluoro-4-isothiocyanatophenyl)-3-((4-pentylphenyl)- ethynyl)-1,2-dihydronaphthalene

[1226] Step 3.1: 7-bromo-3-((4-pentylphenyl)ethynyl)-1,2-dihydronaphthalene

[1227]

[1228] A solution of 6-bromo-3,4-dihydronaphthalen-2-yl trifluoromethanesulfonate (CAS 1013891-56-9) (5.5 g, 15 mmol) and 1-ethynyl-4-pentylbenzene (CAS 79887-10-8) (2.7 g, 16 mmol) in THF (50 ml) and triethylamine (25 ml) was treated with bis(triphenylphosphine)palladium(II) chloride (108 mg, 0.2 mmol) and copper(I) iodide (32 mg, 0.2 mmol) under an argon atmosphere and the reaction mixture was stirred at 50 °C for 2 hours. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and extracted with MTB ether and the combined organic phases were washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) and crystallization (isopropanol) to yield 7-bromo-3-((4-pentylphenyl)ethynyl)-1,2-dihydronaphthalene as colorless crystals.

[1229] Step 3.2: 2,6-difluoro-4-(6-((4-pentylphenyl)ethynyl)-7,8-dihydronaphthalen-2- yl)aniline

[1230]

[1231] A solution of potassium carbonate (2.9 g, 21 mmol) in distilled water (15 ml) was added to a solution of 7-bromo-3-((4-pentylphenyl)ethynyl)-1,2-dihydronaphthalene (4.7 g, 12 mmol) in THF (80 ml) at room temperature under an argon atmosphere. The mixture was heated to 60 °C and treated with di-(1-adamantyl)-n-butylphosphine (50 mg, 0.14 mmol) and tris(dibenzylidene-acetone)dipalladium(0) (70 mg, 0.08 mmol). A solution of 2,6-difluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (CAS 939968-08-8) (3.5 g, 12 mmol) in THF (20 ml) was then slowly added and the mixture was stirred at reflux temperature overnight. It was then allowed to cool to room temperature and quenched with brine and MTB ether. The aqueous phase was separated and washed with MTB ether and the combined organic phases were washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) and crystallization (toluene) to give 2,6-difluoro-4-(6-((4-pentylphenyl)ethynyl)-7,8-dihydronaphthalen-2-yl)aniline as a light yellow solid.

[1232] Step 3.3: 7-(3,5-difluoro-4-isothiocyanatophenyl)-3-((4-pentylphenyl)ethynyl)-1,2- dihydronaphthalene

[1233]

[1234] Thionyl chloride (0.9 ml, 11 mmol) was slowly added to a solution of 2,6-difluoro-4-(6-((4-pentylphenyl)ethynyl)-7,8-dihydronaphthalen-2-yl)aniline (3.7 g, 9 mmol) and DABCO (3.0 g, 27 mmol) in dichloromethane (50 ml) at 0 °C under an argon atmosphere and the reaction mixture was stirred at room temperature for 2 hours. It was then quenched with distilled water (1 ml), filtered over silica gel, washed with dichloromethane and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane / chlorobutane) and crystallization (heptane) to give 7-(3,5-difluoro-4-isothiocyanatophenyl)-3-((4-pentylphenyl)ethynyl)-1,2-dihydronaphthalene as a light yellow solid.

[1235] Phase sequence: K 97 N 239 I.

[1236] Δn = 0.5362

[1237] Δε = 20.2

[1238] Synthesis Example 4: 3-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-7-pentyl-1,2- dihydro naphthalene

[1239] Step 4.1 : 4-((6-bromo-3,4-dihydronaphthalen-2-yl)ethynyl)-2,6-difluoroaniline

[1240]

[1241] To a solution of trifluoromethanesulfonic acid 6-bromo-3,4-dihydronaphthalen-2-yl ester (CAS 1013891-56-9) (9.0 g, 24 mmol) and 4-ethynyl-2,6-difluoroaniline (CAS 753501-37-0) (3.8 g, 24 mmol) in THF (90 ml) and triethylamine (45 ml) under an argon atmosphere was added dichlorobis(triphenylphosphine)palladium(II) (180 mg, 0.26 mmol) and copper(I) iodide (50 mg, 0.26 mmol) and the reaction mixture was stirred at 50 °C overnight. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and extracted with MTB ether and the combined organic phases were washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent chlorobutane) to give 4-((6-bromo-3,4-dihydronaphthalen-2-yl)ethynyl)-2,6-difluoroaniline as a light brown solid.

[1242] Step 4.2: 2,6-difluoro-4-((6-pentyl-3,4-dihydronaphthalen-2-yl)ethynyl)aniline

[1243]

[1244] To a solution of 4-((6-bromo-3,4-dihydronaphthalen-2-yl)ethynyl)-2,6- difluoroaniline (8.1 g, 23 mmol) in THF (100 ml) under argon atmosphere was added potassium phosphate monohydrate (11.0 g, 45 mmol), bis(dibenzylidene- acetone)palladium(0) (130 mg, 0.22 mmol) and 2-dicyclohexylphosphino-2',6'- dimethoxybiphenyl (190 mg, 0.45 mmol). A solution of pentylboronic acid (5.5 g, 45 mmol) in THF (10 ml) was then added and the reaction mixture was stirred at reflux temperature overnight. It was allowed to cool to room temperature and quenched with distilled water and MTB ether. The aqueous phase was separated and washed with MTB ether and the combined organic phases were washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent chlorobutane) to give 2,6-difluoro-4-((6-pentyl-3,4-dihydronaphthalen-2- yl)ethynyl)aniline as yellow crystals.

[1245] Step 4.3: 3-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-7-pentyl-1,2- dihydronaphthalene

[1246]

[1247] Thionyl chloride (2.7 g, 23 mmol) was slowly added to a solution of 2,6-difluoro-4-((6-pentyl-3,4-dihydronaphthalen-2-yl)ethynyl)aniline (6.4 g, 18 mmol) and DABCO (5.2 g, 46 mmol) in dichloromethane (100 ml) at 0°C under argon atmosphere and the reaction mixture was stirred at room temperature overnight. It was then quenched with distilled water, filtered over silica gel, washed with dichloromethane and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, eluent heptane) and subsequent crystallization (heptane) to give 3-((3,5-difluoro-4-isothiocyanatophenyl)ethynyl)-7-pentyl-1,2- dihydronaphthalene as yellow crystals.

[1248] Phase sequence: K 57N (46) I.

[1249] Δn = 0.4425

[1250] Δε = 15.9

[1251] The following compounds were obtained analogously to Synthesis Examples 1 to 4:

[1252]

[1253]

[1254]

[1255]

[1256]

[1257]

[1258]

[1259]

[1260]

[1261]

[1262]

[1263]

[1264]

[1265]

[1266]

[1267]

[1268]

[1269]

[1270]

[1271]

[1272] Mixture Example

[1273] Host mixture H1 has the following composition:

[1274]

[1275] The following example mixtures were prepared from host mixture H1 and the compounds according to the application indicated in the table below.

[1276] Comparative Example C1

[1277]

[1278] Example mixture M1

[1279]

[1280] The difference between the example mixture M1 and the comparative example C1 is that the compound PTU-5-S has been replaced by the compound Np(2H)TU-5-S according to the present application. This has the effect that the clearing temperature, the dielectric loss, the tunability and the quality factor are all significantly improved.

[1281] Example mixture M2

[1282]

[1283] Example mixture M3

[1284]

[1285]

[1286] Example mixture M4

[1287]

[1288] Example mixture M5

[1289]

[1290]

[1291] Example mixture M6

[1292]

[1293] Example mixture M7

[1294]

[1295]

[1296] Example mixture M8

[1297]

Claims

1. A compound of formula D in R D represents H, a straight-chain alkyl radical having 1 to 12 C atoms or a branched-chain alkyl radical having 2 to 12 C atoms, or a straight-chain alkenyl radical having 2 to 12 C atoms, or a branched-chain alkenyl radical having 3 to 12 C atoms, or a straight-chain alkynyl radical having 2 to 12 C atoms or a branched-chain alkynyl radical having 4 to 12 C atoms, wherein one or more CH2- groups may be replaced by and one or more non-adjacent CH2- groups may be replaced by O or represent a group R P , R P Indicates halogen, CN, NCS, R F -、R F -O- or R F -S-, where R F represents a fluorinated alkyl group having 1 to 9 C atoms, Z D1 , Z D2 , Z D3 and Z D4 Identically or differently represent -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -N=N-, -C=NN=C-, -CH=N-, -N=CH-, -C≡C-, -C≡CC≡C- or a single bond, wherein Z D1 represents -O-, -S-, -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -C2F4-, -CH2CF2-, -CF2CH2-, -CH=CH-CH2O-, -CH=CH-CO-O-, -OCH2-CH=CH- or -O-CO-CH=CH-, X D Indicates -C≡C-CN, -NCS or -C≡C-NCS, and represent, identically or differently, a group selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, in which one or two CH groups may be replaced by N and in which one or more H atoms may be replaced by L, b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4′-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, in which one or two CH groups may be replaced by N, one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-, and in which one or more H atoms may be replaced by L, c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L, express wherein one or more H atoms are optionally replaced by L, L, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or in each case optionally fluorinated, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having 1 to 12 C atoms, t1, t2, t3 and t4 are the same or different and are 0, 1 or 2, Where t1+t2+t3+t4 is 1, 2 or 3.

2. The compound according to claim 1, wherein the compound is selected from the group consisting of compounds of formula D-1 and D-2: where R D 、 Z D2 , Z D4 and X D has the meaning given in claim 1, and t2 is 0, 1, or 2, t4 is 0 or 1, And t2+t4 is 1, 2 or 3.

3. The compound according to claim 2, wherein Z D2 and Z D4 The same or different groups represent -CH=CH-, -CF=CF-, -C≡C- or a single bond.

4. Compounds according to one or more of claims 1 to 3, wherein and express where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms or cycloalkyl having 3 to 5 C atoms, where Alternatively expressed in W represents N, CH, CF or C-Cl, and Y 1 and Y 2 represents H, Cl, F, methyl or ethyl, identically or differently.

5. Compounds according to one or more of claims 1 to 4, wherein X D Indicates -NCS.

6. A liquid-crystalline medium comprising one or more compounds of the formula D according to one or more of claims 1 to 5.

7. Liquid-crystalline medium according to claim 6, wherein the medium additionally comprises one or more compounds selected from the group of compounds of the formulae I, II and III: in R 1 represents H, non-fluorinated alkyl having 1 to 12 C atoms or non-fluorinated alkenyl having 2 to 12 C atoms, wherein one or more CH2- groups may be replaced by Replacement, wherein one or more non-adjacent CH2- groups may be replaced by O, n is 0, 1, or 2, and Indicates that each occurrence is independent of the other where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms, Or express wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F, express And among them Alternatively expressed R 2 represents H, non-fluorinated alkyl having 1 to 12 C atoms or non-fluorinated alkenyl having 2 to 12 C atoms, wherein one or more CH2- groups may be replaced by Replacement, wherein one or more non-adjacent CH2- groups may be replaced by O, Z 21 represents trans-CH=CH-, trans-CF=CF-, or -C≡C-, and express where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms, Or express wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F, express where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms, Or express wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or F; R 3 represents H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17 C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, wherein one or more CH2- groups may be replaced by Alternative, Z 31 and Z 32 One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other independently thereof represents -C≡C-, trans-CH=CH-, trans-CF=CF- or a single bond, and Independently express where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms, wherein one or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or by F, And among them Alternatively expressed express where R L represents, identically or differently on each occurrence, H or alkyl having 1 to 6 C atoms, Or express One or more H atoms may be replaced by an alkyl group having 1 to 6 C atoms or F.

8. Liquid-crystalline medium according to claim 6 or 7, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae I-1 to I-5: in L 1 , L 2 and L 3 represents H or F identically or differently on each occurrence, and R 1 、 and has the meaning given for formula I in claim 7.

9. Liquid-crystalline medium according to one or more of claims 6 to 8, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae II-1 to II-3: in R 2 、 has the meaning given in claim 7 for formula II.

10. Liquid-crystalline medium according to one or more of claims 6 to 9, wherein the medium comprises one or more compounds of the formula III selected from the compounds of the formulae III-1 to III-6: in Z 31 and Z 32 represents, independently of each other, trans-CH=CH- or trans-CF=CF-, preferably trans-CH=CH-, and in formula III-6, alternatively Z 31 and Z 32 One of them may represent -C≡C- and the other group has the meaning given for formula III in claim 1, R 3 represents a non-fluorinated alkyl or alkoxy group having 1 to 7 C atoms or a non-fluorinated alkenyl group having 2 to 7 C atoms, and and the others are expressed independently of each other in Alternatively expressed 11. The medium according to one or more of claims 6 to 10, wherein the medium comprises one or more compounds selected from the group consisting of formulae IIIa-1, IIIa-2, IIIa-3 and IIIa-4: where R 3 has the meaning as defined in claim 7 for formula III.

12. Liquid-crystalline medium according to one or more of claims 6 to 11, wherein the medium comprises one or more compounds of the formula UI: in R U represents H, a linear or branched non-fluorinated alkyl radical having 1 to 12 C atoms or a non-fluorinated alkenyl radical having 2 to 12 C atoms, wherein one or more CH2- groups may be replaced by substitution, wherein one or more non-adjacent CH2- groups may be replaced by O, or represents a group R P , R P Represents halogen, CN, NCS, fluorinated alkyl, R F -O- or R F -S-, where R F represents a fluorinated alkyl or fluorinated alkenyl group having up to 9 C atoms, Z U1 represents -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or -C≡CC≡C-, X U1 、X U2 Identically or differently represent Cl or F, and represents a group selected from the following group: a) the group consisting of 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene, in which one or two CH groups may be replaced by N and in which one or more H atoms may be replaced by L, b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-5,8-diyl, decahydronaphthalene-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4′-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, in which one or two CH groups may be replaced by N, one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-, and in which one or more H atoms may be replaced by L, c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L, L, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or in each case optionally fluorinated, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having 1 to 12 C atoms, u is 0 or 1, v is 0 or 1, The compound of formula UI is not included in the compounds of formula I, II and III according to claim 7.

13. An electronic component comprising: a first substrate and a second substrate facing each other, a liquid crystal layer sandwiched between the substrates, and electrodes disposed on each substrate or two electrodes disposed on only one of the substrates for providing a potential on the liquid crystal layer to drive the liquid crystal in a predetermined configuration. It is characterized by The liquid-crystal layer comprises a liquid-crystal medium according to one or more of claims 6 to 12 .

14. The component according to claim 13, wherein the component is configured for use in high-frequency technology.

15. The component of claim 14, wherein the component is a liquid crystal based antenna element, a phase shifter, a tunable filter, a tunable metamaterial structure, a matching network or a varactor diode.

16. A microwave antenna array, characterized in that It comprises one or more components according to claim 14 or 15.

17. The component of claim 13, wherein the component is a transmissive or reflective spatial light modulator.

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