WO1987002693A1 - Liquid crystal compounds - Google Patents

Liquid crystal compounds Download PDF

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Publication number
WO1987002693A1
WO1987002693A1 PCT/GB1986/000661 GB8600661W WO8702693A1 WO 1987002693 A1 WO1987002693 A1 WO 1987002693A1 GB 8600661 W GB8600661 W GB 8600661W WO 8702693 A1 WO8702693 A1 WO 8702693A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal compound
mesogenic
metal
nitrogen
Prior art date
Application number
PCT/GB1986/000661
Other languages
French (fr)
Inventor
Peter Michael Maitliss
Duncan Watson Bruce
David Allen Dunmur
Original Assignee
The University Of Sheffield
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB858526462A external-priority patent/GB8526462D0/en
Priority claimed from GB858527377A external-priority patent/GB8527377D0/en
Application filed by The University Of Sheffield filed Critical The University Of Sheffield
Publication of WO1987002693A1 publication Critical patent/WO1987002693A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C07F15/0093—Platinum compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals

Definitions

  • This invention relates to liquid crystals and more particularly to liquid crystals containing a transition metal and to ionic liquid crystals.
  • Known liquid crystals containing a transition metal are complexes of the type [(L-H)PdCl] 2 , [(L-H) 2 Cu] 2 , or [(L-H) 2 M] where M represents Cu, Ni, Pd or Pt and L represents a ligand precursor.
  • L represents a ligand precursor
  • ligand precursor which can be a mesogen
  • anionic ligand for example a halide must be lost from the metal.
  • liquid crystal compound formed by coordination of a mesogenic organo nitrogen ligand, via a nitrogen donor atom, or of a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex. Many of these liquid crystals are coloured.
  • the invention also provides a method for preparing a liquid crystal compound by combining a mesogenic organo nitrogen ligand via a nitrcgen donor atom, or a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex .
  • the invention also provides liquid crystal compounds formed, by ionic interaction of mesogenic cations with mesogenic anions.
  • the anion and/or the cation may contain a metal. Alternatively the anion and cation may both be purely organic materials.
  • Organo-nitrogen compounds which can be used in the present invention include nitriles, heterocyclic compounds such as pyridines and amines.
  • the transition metals most usefully employed in the present invention include d-block transition metals.
  • the liquid crystal compound of the invention may be of different types.
  • the first type can be represented by the general formula
  • M represents a metal X represents halide
  • type I compounds are obtained when the metal is palladium (type la) or platinum (type lb).
  • a further type of compound obtainable in accordance with the present invention is represented by the general formula
  • Yet another type comprises the ionic materials represented by the formula
  • L is as defined above, Y is a mesogenic anion and X is a mesogenic cation.
  • a further type of compound is represented by the formula
  • R represents an alkyl or aryl group, for example C 11 H 23 and M is as defined above.
  • the compounds of the present invention are readily synthesised from easily obtainable materials.
  • the compounds are air stable.
  • the liquid crystal compounds of the present invention display a variety of separate phases.
  • the preferred materials of types I, II, III, IV, V and VI showed nematic phases and in some cases smectic phases.
  • the transitions between the phases were in some instances enantiotropic and in other cases monotropic.
  • Mixtures of; compounds for example of type la but derived from different organo-nitrogen mesogens having monotropic phase transitions can be obtained with enantiotropic phase transitions.
  • composition and structure of the compounds was established by elemental analysis (C, H, Cl and N) by 1 H and 13 C NMR spectroscopy and by IR spectroscopy. Phase transition temperatures were measured by hot stage optical microscopy and the mesophases were identified by their optical textures.
  • Molybdenum hexacarbonyl (1 g) was refluxed (4 h) in dry diglyme (38 cm 3 ) with lauric acid (2.25 g) under
  • Rhodium trichloride hydrate (0.18 g), sodium laurate (0.5 g), lauric acid (1.5 g) and ethanol (absolute, 20 cm 3 ) were, refluxed together (1 h) under nitrogen. After cooling the solution was filtered; the ethanolic filtrate was allowed to stand overnight and the green-blue precipitate which formed was collected by filtration and dried under vacuum (20°C/18 h; 65°C/20 h) to give the green-blue complex (VII) [Rh 2 (C 12 H 21 O 2 ) 4 ] (0.12g; 36%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Liquid crystal compounds comprising the product of co-ordination of a mesogenic organonitrogen ligand via a nitrogen donor atom, or of a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex. The invention also includes a liquid crystal compound formed by ionic interaction of a mesogenic cation with a mesogenic anion.

Description

LIQUID CRYSTAL COMPOUNDS
This invention relates to liquid crystals and more particularly to liquid crystals containing a transition metal and to ionic liquid crystals.
Known liquid crystals containing a transition metal are complexes of the type [(L-H)PdCl]2, [(L-H)2Cu]2 , or [(L-H)2M] where M represents Cu, Ni, Pd or Pt and L represents a ligand precursor. In order to form these complexes hydrogen must be lost from the compound L, i.e. the ligand precursor (which can be a mesogen) to form the chelating ligand (L-H). In addition an anionic ligand for example a halide must be lost from the metal. These two requirements limit the ligands and metals from which the liquid crystals can be formed.
According to the present invention there is provided a liquid crystal compound formed by coordination of a mesogenic organo nitrogen ligand, via a nitrogen donor atom, or of a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex. Many of these liquid crystals are coloured.
The invention also provides a method for preparing a liquid crystal compound by combining a mesogenic organo nitrogen ligand via a nitrcgen donor atom, or a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex . The invention also provides liquid crystal compounds formed, by ionic interaction of mesogenic cations with mesogenic anions. The anion and/or the cation may contain a metal. Alternatively the anion and cation may both be purely organic materials.
The invention provides, therefore, a general method for. obtaining a wide variety of liquid crystals having useful properties. Organo-nitrogen compounds which can be used in the present invention include nitriles, heterocyclic compounds such as pyridines and amines. The transition metals most usefully employed in the present invention include d-block transition metals.
The liquid crystal compound of the invention may be of different types. The first type can be represented by the general formula
L2MX2 (I)
where L represents organo-nitrogen mesogen
M represents a metal X represents halide
Preferred embodiments of type I compounds are obtained when the metal is palladium (type la) or platinum (type lb). A further type of compound obtainable in accordance with the present invention is represented by the general formula
LRh(CO)2X (II)
LAuX (III)
where L and X are as defined above.
Yet another type comprises the ionic materials represented by the formula
[L2Ag]+BF4- (IV) [L2Ag] +Y- (V)
X+Y- (VI)
where L is as defined above, Y is a mesogenic anion and X is a mesogenic cation.
A further type of compound is represented by the formula
[(RCOO)4M2] (VII)
where R represents an alkyl or aryl group, for example C11H23 and M is as defined above.
The compounds of the present invention are readily synthesised from easily obtainable materials. The compounds are air stable. The liquid crystal compounds of the present invention display a variety of separate phases. In particular the preferred materials of types I, II, III, IV, V and VI showed nematic phases and in some cases smectic phases. The transitions between the phases were in some instances enantiotropic and in other cases monotropic. Mixtures of; compounds for example of type la but derived from different organo-nitrogen mesogens having monotropic phase transitions can be obtained with enantiotropic phase transitions.
The following Examples further illustrate the invention.
In the Examples the composition and structure of the compounds was established by elemental analysis (C, H, Cl and N) by 1H and 13C NMR spectroscopy and by IR spectroscopy. Phase transition temperatures were measured by hot stage optical microscopy and the mesophases were identified by their optical textures.
EXAMPLE 1
4-Carbonitrile-4'-nonyloxybiphenyl (0.34 cm3, 1.0 mmol) was added to [PdCl2 (PhCN)2] (0.2 g, 0.52 mmol) dissolved in acetone (30 cm3). The solution was stirred (20°C, 2h), the acetone was removed in vacuo, and the residual solid was triturated with ethanol (20 cm ) to give the product, bis (4-carbonitrile-4'-nonyloxybiphenyl) dichloropalladium (la, L = C9H19OC6H6C6H4CN; 0.35g 84%) as orange crystals.
EXAMPLE 2
4-Carbonitrile-4-octylbiphenyl (0.25 ml, 0.9 mmol) and [PtCl2 (PhCN)2] (0.2 g, 0.42 mmol) were refluxed in toluene (50 cm3, 20 h). The toluene was then removed in vacuo, the residue triturated with ethanol, and crystallised from dichloromethane-ethanol to give bis (4-carbonitrile-4'-octylbiphenyl) dichloroplatinum
(lb, L = C8H17C6H4C6H4CN; 0.15 g, 43%) as yellow crystals.
EXAMPLE 3
Addition of 4-carbonitrile-4'-nonyloxybiphenyl
(0.17 g, 0.54 mmol) to a solution of [Rh2(CO)4Cl2] (0.1 g, 0.26 mmol) dissolved in hexane (10 cm3) gave a yellow precipitate. This was filtered off and washed with hexane to give orange cis-dicarbonyl (4-carbonitrile-4'- nonyloxybiphenyl) chlororhodium (0.2 g, 77%)
(II, L = C9H19OC6H4C6H4CN).
EXAMPLE 4
4-Butoxy-4'-stilbazole (0.078 g) was added to a solution of silver tetrafluoroborate (0.03 g) dissolved in dry acetone (5 cm3). A solid slowly precipitated
(over 1 h/20°C). The solvent was then removed in vacuo, to leave a yellow residue which was washed with hexane and air dried to give yellow bis (4-butoxy-4'-stilbazole) silver tetrafluoroborate [IV, L = C4H5OC6H4CH=CHC5H4N;
0.07 g, 67%).
EXAMPLE 5
Molybdenum hexacarbonyl (1 g) was refluxed (4 h) in dry diglyme (38 cm3) with lauric acid (2.25 g) under
N2. A yellow precipitate formed on cooling which was filtered off and washed with diethyl ether under nitrogen to leave yellow crystals. These crystals were dried (under vacuum at 70°C/24 h) to give the compound VII, [Mo2(C12H21O2)43 (1.73 g, 92%).
EXAMPLE 6
Rhodium trichloride hydrate (0.18 g), sodium laurate (0.5 g), lauric acid (1.5 g) and ethanol (absolute, 20 cm3) were, refluxed together (1 h) under nitrogen. After cooling the solution was filtered; the ethanolic filtrate was allowed to stand overnight and the green-blue precipitate which formed was collected by filtration and dried under vacuum (20°C/18 h; 65°C/20 h) to give the green-blue complex (VII) [Rh2(C12H21O2)4] (0.12g; 36%).
EXAMPLE 7
Cetyltrimethylammonium laurylsulphate, compound VI, X+ = [Me3NC16H33] + , Y- = [SO4C12H25]-, was obtained by extracting with dichloromethane an aqueous solution (200 cm3) of cetyltrimethylammonium bromide (2 g) and sodium laurylsulphate (1.6 g).
The properties of specific materials of the invention were investigated and thes results are set out below.
Bis (4-carbonitrile-4'-pentylbiphenyl) dichloropalladium (la, L = C5H11C6H4C6H4CN) melted to give an isotropic fluid at 125°C. On cooling, a monotropic nematic phase was observed at 92°C.
Bis (4-carbonitrile-4'-nonyloxybiphenyl) dichloropalladium (la, L = C9H19OCgH4CgH4CN) melted to give a mesophase at 119°C which persisted until an isotropic liquid was present at 147°C. On cooling from the isotropic liquid, a nematic phase was formed and the material was totally nematic at 130°C.
Bis (4-carb onitrile-4'-octylbiphenyl) dichloroplatinum melted to give a nematic phase at 170°C which turned into an isotropic fluid at 190°C.
The complex cis-dicarbonyl- (4-carbonitrile-4'- nonyloxybiphenyl) chlororhodium melted to give a nematic phase at 52°C which turned into an isotropic liquid at 80°C.
The complex bis (4-butoxy-4'-stilbazole)silver tetrafluoroborate (IV, L = C4H5OC6H4CH=CHC5H4N) melted at 180°C to a smectic phase which on heating to 305°C became an isotropic liquid. Mixtures of (la, L = C3H7C6H10C6H10CN; X = Cl) and
(la, L = C5H11C6H10C6H10CN; X = Cl) showed enantiotropic nematic phases whereas the second component only showed a monotropic nematic phase.

Claims

1. A liquid crystal compound formed by co-ordination of a mesogenic organo nitrogen ligand via a nitrogen donor atom or of a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex.
2. A liquid crystal compound as claimed in Claim 1, having the general formula
L2MX2
where L represents organo nitrogen mesogen M represents a metal and X represents a halide
3. A liquid crystal compound as claimed in Claim 1 having the general formula
LRh(CO)2X
where L represents organo nitrogen mesogen and X represents a halide.
4. A liquid crystal compound as claimed in Claim 1, having the general formula
LAuX
where L represents organo nitrogen, mesogen and X represents a halide.
5. An ionic liquid crystal compound as claimed in Claim 1 having the general formula
[L2Ag]+BF4 -
where L represents organo nitrogen mesogen.
6. An ionic liquid crystal compound as claimed in
Claim 1 having the general formula [L2Ag]+Y-
where L represents organo nitrogen mesogen and Y represents a mesogenic anion.
7. A liquid crystal compound as claimed in Claim 1 having the formula [(RCOO)4M2.
where R represents an alkyl or aryl group and M represents a metal.
8. An ionic liquid crystal compound having the general formula
X+Y-
where X+ represents a mesogenic cation and Y- represents a mesogonic anion.
9. A method for preparing a liquid crystal compound by combining a mesogenic organo nitrogen ligand via a nitrogen donor atom or a lyotropic organic carboxylate with a metal or the metal centre of a transition metal complex.
10. A method for preparing a liquid crystal compound comprising ionic interaction of a mesogenic cation with a mesogenic anion.
PCT/GB1986/000661 1985-10-26 1986-10-27 Liquid crystal compounds WO1987002693A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB858526462A GB8526462D0 (en) 1985-10-26 1985-10-26 Liquid crystal compounds
GB8526462 1985-10-26
GB8527377 1985-11-06
GB858527377A GB8527377D0 (en) 1985-11-06 1985-11-06 Liquid crystal compounds

Publications (1)

Publication Number Publication Date
WO1987002693A1 true WO1987002693A1 (en) 1987-05-07

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EP (1) EP0252925A1 (en)
WO (1) WO1987002693A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU576420B2 (en) * 1985-03-25 1988-08-25 Nippon Sheet Glass Co. Ltd. Electrochromic device
WO2004065523A1 (en) * 2003-01-24 2004-08-05 Merck Patent Gmbh Ionic mesogenic compounds
WO2016063273A1 (en) 2014-10-20 2016-04-28 Gauzy Ltd. Metal organic liquid crystal dyes
US20220050316A1 (en) * 2014-11-06 2022-02-17 Gauzy Ltd. Bistable liquid crystal dispersion devices comprising metal-organic mesogens and applications thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal of the Chemical Society (Chemical Communications) No. 8, 15 April 1986, Royal Society of Chemistry, London (GB) D.W. BRUCE et al.: "Novel Transition Metal Containing Nematic and Smectic Liquid Crystals", pages 581, 582, see the whole article *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU576420B2 (en) * 1985-03-25 1988-08-25 Nippon Sheet Glass Co. Ltd. Electrochromic device
WO2004065523A1 (en) * 2003-01-24 2004-08-05 Merck Patent Gmbh Ionic mesogenic compounds
WO2016063273A1 (en) 2014-10-20 2016-04-28 Gauzy Ltd. Metal organic liquid crystal dyes
US20220050316A1 (en) * 2014-11-06 2022-02-17 Gauzy Ltd. Bistable liquid crystal dispersion devices comprising metal-organic mesogens and applications thereof

Also Published As

Publication number Publication date
EP0252925A1 (en) 1988-01-20

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