EP1362076A1

EP1362076A1 - Metallic thiacalix 4]arene complexes

Info

Publication number: EP1362076A1
Application number: EP02706895A
Authority: EP
Inventors: Stéphane PAROLA; Cédric DESROCHES; Francis Vocanson; Jean Bouix; Roger Lamartine
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Claude Bernard Lyon 1 UCBL
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite Claude Bernard Lyon 1 UCBL
Priority date: 2001-02-23
Filing date: 2002-02-25
Publication date: 2003-11-19
Also published as: US20040127722A1; US6936721B2; FR2821357A1; FR2821357B1; WO2002068521A1

Abstract

The invention relates to novel thiacalix[4]arene derivative complexes having formula (I), wherein R1a, R2a, R3a, R4a, R1b, R2b, R3b and R4b are as defined in claim 1. The invention also relates to the use thereof, particularly for the production of materials having optical limiting properties.

Description

THIACALIX (4) ARENES METAL COMPLEXES

The present invention relates to new metal complexes of thiacalix [4] arene derivatives, in particular with a transition metal, as well as their use, in particular for the manufacture of materials having optical limiter properties.

Certain derivatives of thiacalixarene type are described in the prior art. We can for example cite the patent application published under the number WO 99 19 427 which describes derivatives of formula (A):

in which Y is a bivalent bridging group at least one of said bridging groups being a sulfur atom, R 'is hydrogen, a hydrocarbyl group or a hetero-substituted hydrocarbyl group and n is an integer at least equal to 4.

Note that the only example of compound (A) given is a sulfur-containing dodecylcalix [8] arene. In addition, it is indicated that the derivatives of formula (A) are useful as additives for lubricant.

Other derivatives of thiacalix [4] arene are described in the literature: Lhotak et al. described in Tetrahedron Letters 2000, 41, 9339-9344, in particular the 25,27-dimethoxythiacalix [4] arene and in Tetrahedron Letters 1998, 39, 8915-8918, thiacalix [4] arene derivatives of formula (B): wherein R ' ₅ represents a hydrogen atom or a tert-butyl group and R' ₇ represents a methyl, ethyl, n-propyl or rc-butyl group. These various compounds form, in the solid state, infinite channels.

One of the objectives which the invention proposes to achieve is to develop new thiacalix [4] arene derivatives having in particular the following properties

- good electronic delocalization of π electrons,

- great complexing properties, - significant thermal stability, which makes possible the heat treatment of these compounds and therefore their incorporation in materials, for example in a glass-type matrix.

These compounds are functionalized or easily functionalizable which makes it possible to modulate their properties. The thiacalix [4] arenas according to the invention as well as their metal complexes have third order non-linear optical properties. It should be noted that laser technology has experienced recent and rapid progress, leading to the appearance of new compact high-performance laser systems operating at variable wavelengths. Also, the development of new materials, making it possible to protect equipment, optical sensors and the eye of users against laser attack, is necessary.

Certain thiacalix [4] arene complexes according to the invention with a transition metal have thermochromic properties.

The subject of the present invention is the thiacalix [4] arenes of formula (I): in which :

- Ri _a , R _{2a> 3a} and R _4a , identical or different, each independently represent:

- a hydrogen atom,

- an (Cι-Cι ₂ ) alkyl group,

- a (Cι-Cι ₂ ) alkenyl group,

- A group -SO ₂ -Rι, in which Ri represents a phenyl, benzyl or naphthyl group, unsubstituted or substituted one or more times by a halogen atom, a (Cι-C ₄ ) alkyl group, (Cι- C ₄ ) alkenyl or (Cι-C ₄ ) alkynyl, or else,

- A group -SiR ₂ R ₃ R ₄ , in which R, R and R ₄ each independently represent a (Cι-C ₄ ) alkyl group;

- Rit ,, R ₂ b, R3b and R b, identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom,

- an (Cι-C ₆ ) alkyl group,

a phenylazo group optionally substituted preferably in position 4 by a nitro group,

a group -N = CHR ₅ in which R ₅ represents a (Cι-C) alkyl, pyridyl or phenyl group,

a group -C≡CR ₆ in which R ₆ represents a hydrogen atom, a group (Cι-C ₄ ) alkyl, tri (Cj-C ₄ ) alkylsilyl, phenyl, or a group of formula: where R ₆ 'represents a hydrogen atom or a phenyl optionally substituted in para by a (Cι-C ₆ ) alkyl group,

- a nitro group or, - a group -NR R ₈ , in which R represents a hydrogen atom and

R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a (Cι-C ₄ ) alkyl, pyridyl or phenyl group, it being understood that, when at least one of the groups Rι _a , R ₂ a, 3a and R _4a represents a methyl group, the others representing a hydrogen atom, or else when Rι _a = R _2a = R3a = 4a and represent either a (C -C ₄ ) alkyl group, or a hydrogen atom, then at least one of the substituents Rib, R ₂ b, 3b or R ^ is different from hydrogen or from the tert-butyl group; as well as their salts, solvates and hydrates.

By alkyl is meant a monovalent hydrocarbon radical, linear or branched, saturated.

By alkenyl is meant a monovalent hydrocarbon radical, linear or branched, unsaturated comprising a double bond.

By alkynyl is meant a monovalent hydrocarbon, linear or branched unsaturated radical comprising a triple bond. By (Cι-C ₄ ) alkyl means an alkyl radical comprising from 1 to 4 carbon atoms.

By halogen atom is meant a chlorine, bromine, iodine or fluorine atom. It will be noted that the exclusion introduced into the definition of the compounds of formula (I) is in particular intended to exclude the compounds already described in the prior art, namely in the publications Tetrahedron Letters 1998, 39, 8915-8918 and 2000 , 41, 9339-9344.

According to another of its aspects, the present invention relates to the compounds of formula (I) in which:

- Ri _a , R _2a , R3a and R4a, identical or different, each independently represent:

- a hydrogen atom,

- an (Cι-Cι ₂ ) alkyl group, - a (Cι-Cι ₂ ) alkenyl group, or else,

- A group -SiR ₂ RR, in which R ₂ , R and R ₄ each independently represent a (Cι-C ₄ ) alkyl group;

- R ^, R _2b , R _3b and R ^, identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom,

- an (Cι-C ₆ ) alkyl group,

a group -N = CHR ₅ in which R5 represents a (Cι-C ₄ ) alkyl, pyridyl or phenyl group,

a group -C≡CR ₆ in which R ₆ represents a hydrogen atom, a (Cι-C ₄ ) alkyl, tri (Cι-C) alkylsilyl phenyl group, or a group of formula:

- \ JΓ ^C≡C - ^">' where R ₆ ' represents a hydrogen atom or a phenyl optionally substituted in para by a (Cι-C ₆ ) alkyl group,

- a nitro group or,

- a group -NR R ₈ , in which R ₇ represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, it being understood that, when at least one of the groups Rι _a , R _2a , R _a or R _4a represents a methyl group, the others representing a hydrogen atom, or else when Rι _a = R _2a = R _3a = R _ta and represent either a (C ₂ -C ₄ ) alkyl group or a hydrogen atom, then at least one of the substituents Ri _b , R _2b , R _3b or R _4b is different hydrogen or tert-butyl; as well as their salts, solvates and hydrates.

- Ri _a , R _2a , R3a and R _a , identical or different, each independently represent:

- a hydrogen atom,

- an (Cι-C ₆ ) alkyl group, a group -SO ₂ -Rι, in which Ri represents a phenyl group, unsubstituted or substituted by a (Cι-C ₄ ) alkyl group, or else,

- A group -SiR ₂ R ₃ R, in which R ₂ , R and R ₄ each independently represent a (Cι-C ₄ ) alkyl group; - Ri _b , R2 _b> R3b and R _4b , identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom,

- an (Cι-C ₆ ) alkyl group, - a phenylazo group optionally substituted preferably in position 4 by a nitro group,

a group -N = CHR ₅ in which R ₅ represents a pyridyl group,

a group -C≡CR ₆ in which R ₆ represents a hydrogen atom or a phenyl group, or a group of formula:

where R ₆ 'represents a hydrogen atom or a phenyl optionally substituted in para by a (Cι-C) alkyl group,

- a nitro group or,

a group -NR R ₈ , in which R ₇ represents a hydrogen atom and R ₈ represents a hydrogen atom or a benzoyl group, it being understood that, when at least one of the groups Rj _a , R _2a , R _3a and R _4a represents a methyl group, the others representing a hydrogen atom, or else when Rι _a = R _2a = R _3a = ta and represent either a (C ₂ -C ₄ ) alkyl group or an atom hydrogen, then at least one of the substituents Rib, R _2b , _3b or R _4b is different from hydrogen or from the tez-t-butyl group; as well as their salts, solvates and hydrates.

The compounds of formula (I), in which at least one of the substituents Ri _b ,

R _2b , R ₃ b and R _4b , represents a nitro group, -N = CHR ₅ or -NR ₇ R ₈ , in which R ₇ represents a hydrogen atom and R ₈ represents a hydrogen atom or a group - C (O) R ₅ , with R ₅ chosen from a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, as well as their salts, solvates or hydrates, constitute a further aspect of the invention. The subject of the present invention is also the thiacalix [4] renes of formula (la):

in which Rι _a , R2a, Rib and R ₂ b are as defined above; as well as their salts, solvates or hydrates.

Also forming an integral part of the invention, the thiacalix [4] arenes of formula (la) in which R _{) a} represents a hydrogen atom or a (Cι-Cι ₂ ) alkyl or (Cι-Cι ₂ ) alkenyl group and R _2a represents a hydrogen atom or a group (Cι-Cι ₂ ) alkyl, (Cι-Cι ₂ ) alkenyl, -SO ₂ -Rι or -SiR ₂ R3R ₄ ; Ri, R ₂ , R3 and i being as defined above; as well as their salts, solvates and hydrates.

According to another of its aspects, the invention relates to the thiacalix [4] arenas of formula (Ib):

in which R] _a , R _2a and Rib are as defined above for (I) and (la); as well as their salts, solvates and hydrates.

According to a subsequent aspect, the subject of the invention is the thiacalix [4] arene derivatives of formula (Ie): in which Rι _a and R ^ are as defined above for (I) and (la); as well as their salts, solvates and hydrates.

The present invention also relates to the thiacalix [4] arenas chosen from:

- 5,11,17,23-Tétraiodo-25,26,27,28-tétrahydroxythiacalix [4] arène, - 5,11,17,23-Tétrabromo-25,26,27,28-tétrahydroxythiacalix [4] arène, -5,11,17,23-Tetra (tert-butyl) -25-propoxy-26,27,28-trihydroxythia- calix [4] arene, -5,11,17,23-Tetra (tert-butyl) - 25,27-di (tert-butyldimethylsiloxy) -26,28-di- hydroxythiacalix [4] arene,

- 5,11,17,23-Tetra (te7-t-butyl) -25,26,27,28-tetrahexyloxythiacalix [4] arene, - 5,11,17,23-Tetrakis (phenylazo) -25,26, 27,28-tetrahydroxythiacalix [4] arene, -5,11,17,23-Tetrakis (4-nitrophenylazo) -25,26,27,28-tetrahydroxythiacalix [4] arene,

-5,11,17,23-Tetra (tert-butyl) -25,27-di (4-toluenesulfonyloxy) -26,28-di- hydroxythiacalix [4] arene, - 5,11,17,23-Tetranitro- 25,26,27,28-tetrahydroxythiacalix [4] arene, - 5, ll tetrachlorhydrate, 17,23-tetraamino-25,26,27,28-tetrahydroxythiacalix [4] arene,

- 25,27-Di (4-toluenesulfonyloxy) -26,28-dihydroxythiacalix [4] arene, - 25,27-Di (tert-butyldimethylsiloxy) -26,28-dihydroxythiacalix [4] arene, -5, ll, 17 , 23-Tetrakis (phenylazo) -25,27-di (4-toluenesulfonyloxy) -26,28-di- hydroxythiacalix [4] arene, - 5,11,17,23-Tetrakis (4-nitrophenylazo) -25,27 -di (4-toluenesulfonyloxy) -

26,28-dihydroxythiacalix [4] arene, - 5,17-Diiodo-25,26,27,28-tetrahydroxythiacalix [4] arene, - 5,17-Dibromo-25,26,27,28-tetrahydroxythiacalix [4] arene,

- 5.1 l, 17.23-Tetra (4-pyridylimino) -25,26,27,28-tetrahydroxythiacalix [4] arene,

- 5.1 l, 17.23-Tetra (phenylethynyl) -25,26,27,28-tetrahydroxythiacalix [4] arene,

- 5.1 l, 17.23-Tetraethynyl-25,26,27,28-tetrahydroxythiacalix [4] arene.

The different conformers of the compounds of formulas (I), (la), (Ib) and (le), namely cone conformation, partial cone, 1,2-altemé, 1,3-alterné (Tetrahedron 1999, 40, 373 -376) are an integral part of the invention.

Generally, the thiacalix [4] arenes according to the present invention can be prepared according to methods analogous to those used, for example for the synthesis of the 25,26,27,28-tetrahydroxythiacalix [4] arene described in particular in Tetrahedron Letters , 1998, 39, 2311-2314, or for the synthesis of 5,11,17,23 -tetra- (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene; or else, the compounds according to the invention can be obtained by total or partial functionalization of these known compounds used as starting materials.

The compounds of formula (I) may contain precursor groups of other functions which will be generated subsequently in one or more other stages.

The compounds of formula (I) in which Rι _a , R _2a , R _3a and / or R _4a are different from hydrogen can be obtained from the corresponding compounds in which the said group (s) R] _a , R _2a , R _3a and / or R _4a are a hydrogen atom by total or partial functionalization of the hydroxyl function in the presence of a base by the action respectively of a halogen derivative of type Hal-R 'ι _a , Hal-R' _a , Hal-R ' _3a and / or Hal-R' _4a in which Hal represents a halogen atom, for example a chlorine or iodine atom and R'ι _a , R '2a, ^* 3a and R' _4a respectively represent Rj _a , R _a , R _3a or R _4a or a precursor group of the latter.

To obtain the functionalization -O (Cι-Cι ₂ ) alkyl, we will operate, for example, in the presence of the number of suitable equivalents of a base of alkali metal carbonate type such as potassium carbonate, cesium or sodium in the reflux acetone.

To obtain the functionalization -OSiR ₂ R ₃ R ₄ , R ₂ , R ₃ , Rj. being as defined for (I), one will operate, for example, in the presence of imidazole. To obtain the functionalization -OSO2-R1, Ri being as defined for (I), we will operate, for example, in the presence of an amino type base such as triethylamine in toluene at reflux.

The compounds (I) in which Rib, R ₂ b, R3b and / or ib represent a group different from hydrogen are, for example, fully or partially functionalized, starting from the corresponding thiacalixarene in which the said compound (s) ) group (s) Ri _b , R _2b , R _3b and / or i _b represent hydrogen or a precursor group of the desired function.

Details on these functionalization methods will be given in the examples which follow.

The compounds (I) in which Rib, R ₂ b, R3b and / or R4b represent an alkynyl derivative, can be synthesized:

- or when the alkynyl derivative is of the -C≡CR ₆ type in which R ₆ represents a (Cι-C ₄ ) alkyl, tri (Cι-C ₄ ) alkylsilyl, phenyl or a group of formula:

where R ₆ 'is as defined above for (I), starting from the corresponding compound (I) in which the said group (s) Rib, R2 _b , R _3b , and / or R _4b represent a halogen atom, by the action of the HC≡CR ₆ derivative, R ₆ being as defined above, in the presence of tri- or diethylamine and a palladium catalyst, according to the Sonogashira reaction, as described for example, in Tetrahedron Letters, 1975, 50, 4467-4470 or EUT. J. Org. Chem. 2000, 3679-3681;

- or when the alkynyl derivative is -C≡CH, from the corresponding compound (I) in which the said group (s) Rib, R2 _b> R _3b and / or i _b represent a group - C≡CR ₆ , with R ₆ being a tri (Cι.C ₄ ) alkylsilyl group, by action of potassium fluoride according to Chem. Common. 2000, 1513-1514.

The method described by Z.-T. Huang et al. in Synthetic Communications, 1997, 27 (21), 3763-3767, for the synthesis of /? - nitrocalixarenes by nitration of the corresponding calixarenes is carried out by action of potassium nitrate and aluminum trichloride in acetonitrile at 0 ° C These operating conditions do not not allow the compounds (I) according to the invention to be synthesized, in which Rib, R2b, R _3b and / or i represent a nitro group.

It has been demonstrated that, surprisingly, the action of nitrogen dioxide or dinitrogen tetroxide in the presence of an ethereal solvent allows the synthesis of the compounds of formula (I) comprising a nitro function.

Also, the subject of the present invention is a process for preparing the compounds of formula (I) in which at least one of the substituents Rib, R2b, R3b or

R _4b represents a nitro group, -N = CHR ₅ or -NR ₇ R ₈ , in which R ₇ represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (Cι-C) alkyl, pyridyl or phenyl, characterized in that: a) if Rib, R2 _b> R3b and / or R ₄ b represent a nitro group, the compound (I) is obtained by nitration of the corresponding thiacalix [4] arene in which the said group (s) Ri _b , R _2b , R _3b and / or R represent a hydrogen atom, by the action of nitrogen dioxide or tetroxide dinitrogen in the presence of an ethereal solvent; b) if Rib, R ₂ b, R3b and / or R ₄ b represent an amino group, the compound (I) is obtained by reduction of the corresponding compound (I) in which the said group (s) Rib, R2b, R3b and / or ib represent a nitro group; c) if Rib, R2 _b , R ₃ b and / or R _4b represent a group -N = CHR ₅ , R ₅ representing a group (Cι-C ₄ ) alkyl, phenyl or pyridyl, the compound (I) is prepared for starting from the corresponding compound (I) in which the said group (s) Rib, R _2b , R _3b and / or R _b represent an amino group, by the action of an aldehyde R ₅ -CHO or d 'a ketone R ₅ -C (O) R _> R ₅ and R ₉ , identical or different, representing independently of one another, a group (Cι-C ₄ ) alkyl, pyridyl or phenyl; d) if Rib, R2b _> R3b and / or R ₄ b, represent a group -NHC (O) R ₅ in which R ₅ represents a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, the compound (I) is obtained from the corresponding compound (I) in which Ri _b , R2b, R3b and / or R _b represent an amino group, by action of the acid halide Hal-C (O) R ₅ in which Hal is an atom halogen and R ₅ is as defined above.

For the synthesis described in a), it is possible to use dimerized nitrogen dioxide also called dinitrogen tetroxide. This nitrogen dioxide forms a complex with the ether used which can be for example di, tri or tetraglyme or a crown ether.

Commercial nitrogen or one prepared in situ will be used, for example by the action of a nitrate of the alkali metal nitrate type such as potassium nitrate in the presence a Lewis acid such as aluminum trichloride. The nitrogen dioxide / ether complex can be synthesized in situ or previously prepared by bubbling nitrogen dioxide in the cold ethereal solvent. We can in particular refer to Journal of Molecular Structure, 1988, 178, 135. For the synthesis described in b), we can use reducing couples of the tin / hydrochloric acid or zinc / acetic acid type.

For the synthesis described in c), it will preferably be carried out in an acid medium, for example in the presence of glacial acetic acid according to the method described by Angew. Chem. Int. Ed. Engl. 1996, 35 (5), 538-540. For the synthesis described in d), reference may be made to J. Chem. Soc. Perkin Trans

2, 1996, 1175.

The functional groups, optionally present in the compounds of formula (I), (la), (Ib) (le) and in the reaction intermediates, can be protected, either permanently or temporarily, by protecting groups which ensure a unique synthesis of the expected compounds. The protection and deprotection reactions are carried out according to techniques well known to those skilled in the art. Those skilled in the art will be able to choose the appropriate protecting groups.

The compounds (I) are isolated and purified, by means of conventional separation techniques: it is possible, for example, to use recrystallizations or else conventional techniques of chromatography on chiral or non-chiral phase.

The subject of the present invention is also the complexes (II) of the compounds of formula (I), (la), (Ib) and (le) with a metal and in particular a transition metal with varying degrees of oxidation. As transition metal, mention may, for example, be made of: copper, palladium, mercury, gold and more preferably, silver, zinc, platinum or lead.

These complexes (II) are obtained according to techniques well known to those skilled in the art, for example, by adding a metal salt to the thiacalix [4] arene of formula (I) in solution in an appropriate organic solvent, by for example, tetrahydrofuran, chloroform or pyridine.

The complexes according to the invention are, for example, capable of being obtained by reaction of a thiacalix [4] arene of formula (I) with a metal derivative of the type: AgSO ₃ CF ₃ , zinc chloride (II), copper (II) chloride, Trans- [PtCl (PEt ₃ ) ₂ (C≡C- phenyl)] or Trans- {PtCl (PEt ₃ ) ₂ [C≡C- (4-pentylphenyl)]} or another platinum complex comprising another phosphine of trialkylphosphine type and / or a phenyl group differently substituted in position 4 with another alkyl group, this list being in no way limiting. The compounds of formula (I) as well as their metal complexes (II), according to the invention, have third-order non-linear optical properties.

The optical limitation measurements were carried out using a measurement bench of the same type as those previously described by: D. Vincent in Nonlinear Optics 1999, 21, 413-422 and DD James, KJ McEwan in Nonlinear Optics, 1999, 21, 377-389. For an incident laser beam of variable energy (0-400 μJ), maximum transmitted energies ranging from 100 μJ to 5 μJ have been measured for the compounds giving the best results.

The derivatives according to the invention are therefore particularly advantageous and can be used in particular as optical limiters. They may be used for the manufacture of materials having optical limiter properties. They can be incorporated into glass-type matrices, using, for example, the sol-gel process (CJ Brinker, GW Scherer, Sol-Gel Science. The Physics and Chemistry of Sol-Gel Processing, Académie Press, 1990 and LC Klein , Sol-Gel Optics: Processing and Applications, Kluwer Académie Publishers, 1994) to develop protective materials against lasers.

The complexes (II) according to the invention with zinc, copper or nickel are colored compounds which have advantageous coloring properties as a function of the temperature. For example, the compound IL 5 (example 5B) changes from the purple color to a deep burgundy color as soon as the temperature reaches 25 ° C. This transformation is reversible and the compound regains its initial coloration on cooling. The compound is stable over time and can undergo a large amount of color change cycles. This was the subject of a study by Differential Calorimetric Analysis (DSC820 Mettler Toledo) which highlighted a phase transition peak between 25 and 40 ° C corresponding to the described phenomenon of color change.

They can therefore be used for the manufacture of thermochromic materials.

The thiacalix [4] arenas (I) according to the invention can be used for the treatment of water, in particular they can make it possible to selectively extract organic compounds (Chemistry Letters, 1999, 777) or cations (Tetrahedron Letters 1998, 39, 7559 and 2001, 42, 1021).

Similarly, certain thiacalix [4] arenas (I) and their metallic complexes (II), by virtue of their second order nonlinear optical properties, could be used as frequency doublers (Angew Chem. Int. Ed. Engl, 1992, 31 (8), 1075).

The examples which follow illustrate the invention without however limiting it.

The nuclear magnetic resonance (NMR) spectra were performed, at 300 MHz and at 25 ° C and the chemical shifts are expressed in ppm. The abbreviations used are as follows: s = singlet, m = multiplet, d = doublet, t = triplet, sex = sextuplet.

EXAMPLES

A - THIACALIX [4] ARENES (I) EXAMPLE 1A

5, ll, 17,23-Tetraiodo-25,26,27,28-tetrahydroxythiacalix [4] arene, compound 1.1

1 g of 25,26,27,28-tetrahydroxythiacalix [4] arene (prepared according to Tetrahedron Letters, 1998, 39, 2311 - 2314) is dissolved in 60 ml of dichloromethane. To this solution, 2.979 g of benzyltrimethylammonium dichloroiodate are added. The orange suspension is stirred for 30 minutes then added with 30 ml of methanol, stirred further for 30 minutes and treated with 1.62 g of calcium carbonate. The suspension is stirred for 24 hours at room temperature. After adding 6 ml of concentrated hydrochloric acid and 100 ml of methanol, the suspension is discolored with 160 ml of an aqueous solution of sodium hydrogen sulphate at 10% and then filtered. The residue is washed with approximately 15 ml of 1M hydrochloric acid, 90 ml of water, 10 ml of methanol and 50 ml of dichloromethane to give a white solid (Yield 65%). 1 H NMR (δ, ppm, C ₅ D ₅ N): 7.83 (s, 8H).

EXAMPLE 2 A

5.1 l, 17.23-Tetrabromo-25,26,27,28-tetrahydroxythiacalix [4] arene, compound 1.2

1 g of 25,26,27,28-tetrahydroxythiacalix [4] arene is suspended in 50 ml of acetone. To this suspension, 1.43 g of N-bromosuccinimide are added. The reaction mixture is stirred under nitrogen, protected from light and at room temperature for 24 hours. The solvents are evaporated, then the solid obtained is washed with approximately 50 ml of water, 20 ml of methanol and 20 ml of dichloromethane. The light brown residue obtained is taken up in 10 ml of pyridine and then precipitated with acetonitrile to give a white powder (Yield 60%).

It is possible to use 2-butanone instead of acetone as a solvent. 1 H NMR (δ, ppm, C ₅ D ₅ N): 7.83 (s, 8H); 12.34 (s, 4H).

EXAMPLE 3A 5, 11, 17,23-Tetra (tert-butyl) -25-propoxy-26,27,28-trihydroxythiacalix [4] arene, compound 1.3

0.3 g of 5, ll, 17.23-tetra (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene (prepared according to Tetrahedron Letters, 1997, 38 (22), 3971-3972) are suspended in 20 ml of acetone 0.191 g of potassium hydrogen carbonate are added. The suspension is stirred at reflux under an inert atmosphere for approximately 30 minutes and then 0.16 ml of ra-propyl iodide are added. The suspension is stirred for approximately 24 hours at reflux and then the solvents are evaporated. The residue is taken up in 90 ml of dichloromethane and acidified with 30 ml of 1M hydrochloric acid. The organic phase is washed with 30 ml of saturated sodium chloride solution and twice 30 ml of water, then dried over sodium sulfate. The organic phase is concentrated and then precipitated with methanol. The yellow powder obtained is recrystallized from a chloroform / methanol mixture to give colorless crystals (Yield 60%). 1 H NMR (δ, ppm, CDC1 ₃ ): 0.80 (s, 9H); 1.16 (t, 3H); 1.22 (s, 9H); 1.34 (s, 18H); 2.06 (sex, 2H); 4.45 (t, 2H); 6.96 (s, 2H); 7.66 and 7.64 (s, 4H); 7.97 (s, 2H).

EXAMPLE 4A

5, ll, 17,23-Tetra (tert-butyl) -25,27-di (tert-butyldimethylsiloxy) -26,28- dihydroxythiacalix [4] arene, compound 1.4

0.5 g of 5, ll, 17.23-tetra (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene are dissolved in 40 ml of dichloromethane. 0.1 g of imidazole and 1.255 g of tert-butyldimethylsilane chloride are added to the solution. The solution is stirred for about 24 hours at room temperature, then acidified with 40 ml of 1M hydrochloric acid. The organic phase is washed with 30 ml of saturated solution in sodium chloride and twice 30 ml of water then dried over sodium sulfate. The organic phase is concentrated, then precipitated with methanol. The product obtained can then be recrystallized from a chloroform / methanol mixture to give a white powder (Yield 90%). 1 H NMR (δ, ppm, CDC1 ₃ ): 0.33 (s, 12 H); 0.85 (s, 18H); 1.19 (s, 18H); 1.31 (s, 18H); 7.06 (s, 4H); 7.62 (s, 4H).

EXAMPLE 5A

5, ll, 17,23-Tetra (tert-butyl) -25,26,27,28-tetrahexyloxythiacalix [4] arene, compound 1.5

0.13 g of 5.1 l, 17.23-tetra (tert-butyl) -25.26.27.28-tetrahydroxythiacalix [4] arene are suspended in 50 ml of acetone. 2.788 g of potassium carbonate are added to the mixture which is heated to reflux and under an inert atmosphere until clarification. 3ml of 1-iodohexane are added. The mixture is heated at reflux for about 24 hours. The solvents are evaporated under reduced pressure then the residue obtained is taken up in 40 ml of chloroform. This organic phase is then washed with approximately 40 ml of 1M hydrochloric acid, 40 ml of saturated sodium chloride solution and 2 times 40 ml of water. The organic phase is dried over sodium sulfate and then the solvents are evaporated under reduced pressure. The crude powder is recrystallized from a chloroform / methanol mixture to give a white powder (Yield 65%).

1 H NMR (δ, ppm, CDC1 ₃ ): 0.85 (t, 12H); 0.99 to 1.14 (m, 32H); 1.27 (s, 36H); 3.81 (t, 8H); 7.30 (s, 8H).

EXAMPLE 6A

5, ll, 17,23-Tetrakis (phenylazo) -25,26,27,28-tetrahydroxythiacalix [4] arene, compound 1.6 a) Benzene diazonium tetrafluoroborate

4.55 ml of aniline are added to 12.6 ml of concentrated hydrochloric acid and 3.65 g of sodium nitrite at a temperature of 0 ° C. A solution of 7.6 g of sodium tetrafluoroborate in 15 ml of water is added. The white precipitate formed is filtered and then washed with 5 ml of ice water, 3 ml of ethanol and 5 ml of ether. diethyl. The product is then dried on filter paper for 12 hours (Yield 70%). b) 0.5 g of 25,26,27,28-tetrahydroxythiacalix [4] arene and 1.6 g of benzenediazonium tetrafluoroborate are dissolved in 20 ml of tetrahydrofuran. 1 ml of pyridine is added at 0 ° C and the reaction mixture is stirred for 16 hours at room temperature, then 50 ml of methanol are added to obtain a yellow precipitate. The precipitate obtained is washed successively with methanol and with diethyl ether and recrystallized from a pyridine / methanol mixture (Yield 64%). Η NMR (δ, ppm, C ₅ D ₅ N): 7.32 (t, 4H); 7.41 (t, 8H); 7.90 (d, 8H); 8.54 (s, 8H); 14.6 (s, 4H).

EXAMPLE 7A

5, ll, 17,23-Tetrakis (4-nitrophenylazo) -25,26,27,28- tetrahydroxy thiacali [4] arene, compound 1.7 a) 4-nitrobenzene diazonium tetrafluoroborate

17 g of 4-nitroaniline are dissolved hot in 65 ml of 6 M hydrochloric acid. After cooling the mixture to 0 ° C, 9 g of sodium nitrite and then 20 g of sodium tetrafluoroborate are added. The precipitate is filtered and washed successively with an aqueous solution of sodium tetrafluoroborate at 5%, ethanol and diethyl ether. Finally the product is dried on filter paper (Yield 97%). b) 0.35 g of 25,26,27,28-tetrahydroxythiacalix [4] arene and 1.4 g of 4-nitrobenzenediazonium tetrafluoroborate are dissolved in 20 ml of tetrahydrofuran. 1 ml of pyridine is added at 0 ° C. The reaction mixture turns orange and a slight precipitation appears. After two days, the precipitate is filtered and washed successively with cold tetrahydrofuran and methanol. The precipitate obtained is recrystallized from pyridine to give red crystals. Η NMR (δ, ppm, C ₅ D ₅ N): 8.17 (s, 4H); 8.29 and 7.86 (2d, 2 x 8H); 8.60 (s, 8H).

EXAMPLE 8A

5, ll, 17,23-Tetra (tert-butyl) -25,27-di (4-toluenesulfonyloxy) -26,28- dihydroxythiacalix [4] arene, compound 1.8 0.5 g of 5, ll, 17,23-tetra (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene are dissolved in 20 ml of toluene at reflux under a nitrogen atmosphere. 0.926 g of 4-toluenesulfonyl chloride and 1.5 ml of triethylamine are added to the reaction mixture. The reaction mixture is heated at reflux for 6 hours then is slowly cooled to room temperature. The solvents are evaporated and the brown residue obtained is taken up with 40 ml of dichloromethane, washed with three times 30 ml of IN hydrochloric acid and four times 30 ml of water, then dried over sodium sulfate. After filtration, evaporation of the solvents and addition of methanol, a white powder precipitates. The powder obtained is recrystallized from a dichloromethane / methanol mixture. (Yield 73%).

1H NMR (δ, ppm, CDC1 ₃ ): 1.29 and 0.84 (s, 36H); 2.49 (s, 6H); 7.01 (s, 4H); 7.60 (s, 4H); 7.86 and 7.36 (d, 8H);

EXAMPLE 9A 5, 11, 17,23-Tetranitro-25,26,27,28-tetrahydroxythiacalix [4] arene, compound 1.9

0.6 g of 25,26,27,28-tetrahydroxythiacalix [4] arene are suspended in 20 ml of diethylene glycoldimethyl ether (diglyme), 0.9 g of potassium nitrate and 3.16 g of aluminum trichloride are added to the suspension. The reaction is slightly activated by heating until a brown color appears, then stirred for 12 hours at room temperature. The suspension is hydrolyzed with 90 ml of water. The organic phase is extracted with 2 times 30 ml of ethyl acetate. The 2 organic fractions are combined and then dried over sodium sulfate. The solvents are evaporated under reduced pressure, then a precipitate is obtained with approximately 50 ml of diethyl ether. The powder obtained is purified by chromatography on a column of silica gel, eluting with a chloroform / methanol mixture, 713 (v / v) to give a yellow solid (yield 35%). 1H NMR (δ, ppm, CD ₃ CN): 8.44 (s, 4H).

EXAMPLE 10A 5, ll, 17,23-tetraamino-25,26,27,28-tetrahydroxythiacalix [4] arene tetrachlorhydrate, compound 1.10

0.5 g of compound 1.9 are suspended in 20 ml of concentrated hydrochloric acid. To this suspension, 2 g of metallic tin are added. The mixture reaction is heated at reflux for 1 hour. The white suspension is cooled in an ice bath and then filtered. The white precipitate is washed with cold hydrochloric acid and then with diethyl ether (quantitative yield).

1 H NMR (δ, ppm, (CD ₃ ) ₂ SO): 7.44 (s, 8H); 9.92 (s, 4H).

EXAMPLE 11 A

25,27-Di (4-toluènesuIfonyloxy) -26,28-dihydroxythiacalix [4] arene, compound 1.11

Prepared according to the procedure described in EXAMPLE 8A, starting from the 25,26,27,28-tetrahydroxythiacalix [4] arene.

EXAMPLE 12A

25,27-Di (tert-butyldimethylsiloxy) -26,28-dihydroxythiacalix [4] arene, compound

1.12

Prepared according to the same procedure as EXAMPLE 4A, starting from the 25,26,27,28-tetrahydroxythiacalix [4] arene.

1 H NMR (δ, ppm, CDC1 ₃ ): 0.33 (s, 12H); 1.15 (s, 18H); 6.07 (d, 4H); 6.43 (t, 2H);

6J9 (t, 2H); 7.60 (d, 4H)

EXAMPLE 13A 5, 11, 17,23-Tetrakis (phenylazo) -25,27-di (4-toluènesuIfonyloxy) -26,28- dihydroxythiaca! Ix [4] arene, compound 1.13

Prepared according to the procedure described in EXAMPLE 8A, starting from compound 1.6.

EXAMPLE 14A 5, 11, 17,23-Tetrakis (4-nitrophenylazo) -25,27-di (4-toluènesulfonyIoxy) -26,28- dihydroxythiacalix [4] arene, compound 1.14

Prepared according to the procedure described in EXAMPLE 8A, starting from compound 1.7.

EXAMPLE 15A

5,17-Diiodo-25,26,27,28-tetrahydroxythiacalix [4] arene, compound 1.15 Prepared by internally forming 5,17-diiodo-25,27-di (tert-butyldimethylsiloxy) -26,28-dihydroxythiacalix [ 4] arene according to the procedure described in EXAMPLE 1A, starting from compound 1.12 and 2.1 equivalents of benzyltrimethylammonium dichloroiodate which is then treated with fluoride potassium in the presence of crown ether (18-crown-6) (G. Stork, PF Hudrlik, J. Am. Chem. Soc, 60, 4462, 1968; CL. Liotta, PH Harris, J. Am. Chem. Soc , 96, 2250, 1974) or with tetrabutylammonium fluoride in tetrahydrofuran (EJ Corey, A. Nenkateswarlu, J. Am. Chem. Soc, 94, 6190, 1972).

EXAMPLE 16A

5,17-Dibromo-25,26,27,28-tetrahydroxythiacaIix [4] arene, compound 1.16 Prepared according to the procedure described in EXAMPLE 15 A, with 2.1 equivalents of N-bromosuccinimide.

The EXAMPLES according to the invention are presented in TABLE 1 below.

TABLE 1 (CONTINUED 1)

TABLE 1 (CONTINUED 3)

EXAMPLE 19A 5, 11, 17,23-Tetrabromo-25,26,27,28-tetrapropoxythiacalix [4] arene, compound 1.19

1 g of 5, ll, 17,23-tetrabromo-25,26,27,28-tetrahydroxythiacalix [4] arene (compound 1.2) is suspended in 60 ml of acetone. To this suspension, 3.2 g of cesium carbonate are added. The mixture is heated to reflux under nitrogen until it becomes clear, then 1.2 ml of 1-iodopropane are added. The mixture is heated at reflux for about 24 hours. The solvents are evaporated under reduced pressure then the residue obtained is taken up in 90 ml of chloroform. This organic phase is then washed with approximately 40 ml of 1M hydrochloric acid, and 2 x 40 ml of water. The organic phase is dried over sodium sulfate and then the solvents are evaporated under reduced pressure. The crude powder was purified by chromatography on silica (silica, CHCl 2 _3/8 hexane) - Yield 80%

EXAMPLE 20A

5, ll, 17,23-tetraiodo-25,26,27,28-tetrapropoxythiacalix [4] arene (2), compound 1.20

1 g of 5, ll, 17,23-tetraiodo-25,26,27,28-tetrahydroxythiacalix [4] arene (compound 1.1) is suspended in 60 ml of acetone. To this suspension 2.6 g of cesium carbonate are added. The mixture is heated to reflux under nitrogen until it becomes clear, then 1 ml of 1-iodopropane is added. The mixture is heated to reflux for approximately 24 hours. The solvents are evaporated under reduced pressure then the residue obtained is taken up in 90 ml of chloroform. This organic phase is then washed with approximately 40 ml of 1M hydrochloric acid, and 2 x 40 ml of water. The organic phase is dried over sodium sulfate and then the solvents are evaporated under reduced pressure. The crude powder is purified by chromatography on silica (silica, 2chloroform / 8 hexane) - Yield 75%. EXAMPLE 21A

5, ll, 17,23-tetratrimethylsiIylethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene (3), compound 1.21

WALNUT 1:

0.5 g of 5.11,17.23-tetraiodo-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 1.20) are suspended in 20 ml of deoxygenated triethylamine. To this suspension 30 mg of dichlorobistriphenylphosphine palladium (II), 4 mg of cuprous iodide and 0.2 g of trimethylsilylacetylene are added. The reaction medium is heated at 40 ° C for 24 hours, then treated with HCl (10%) and extracted with 40 ml of ethyl acetate.

The organic phase is washed with water (2 x 30 ml) and then dried over Νa SO. Finally the product is purified by column chromatography (silica, 8 Hexane / 2 Chloroform) -Rdt 75%.

WALNUT 2:

0.5 g of 5.11,17.23-tetrabromo-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 1.19) are suspended in 20 ml of deoxygenated triethylamine. To this suspension 30 mg of dichlorobistriphenylphosphine palladium (II), 5 mg of cuprous iodide and 0.25 g of trimethylsilylacetylene are added. The reaction medium is heated at 40 ° C for 24 hours, then treated with HCl (10%) and extracted with 40 ml of ethyl acetate.

The organic phase is washed with water (2 x 30 ml) and then dried over Νa ₂ SO ₄ . Finally the product is purified by column chromatography (silica, 8 Hexane / 2 Chloroform) -Rdt 70%.

EXAMPLE 22A 5, 11, 17,23-Tetraethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene, compound 1.22

0.5 g of 5, ll, 17,23-tetratrimethylsilylethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 1.21) are dissolved in 20 ml of tetrahydrofuran. 1.2 g of tetrabutylammonium trihydrate fluoride are added. The solution is stirred for 2 h under an inert atmosphere, then evaporated to dryness. The residue is taken up in chloroform. The organic phase is washed with HCl IM, then H ₂ O and dried over Na ₂ SO ₄ . After evaporation of the solvents, the product is purified by column chromatography (silica, 8 hexane / 2 chloroform) - Yield 90%.

COMPOUND 23A

5, ll, 17,23-Tetraphenylethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene, compound 1.23

0.5 g of 5, ll, 17,23-Tetraiodo-25,26,27,28-tetrapropoxythiacalix [4] arene are suspended in 20 ml of oxygen-free triethylamine. To this suspension 20 mg of dichlorobistriphenylphosphine palladium (II), 4 mg of cuprous iodide and 0.2 g of phenylacetylene are added. The reaction mixture is heated at 40 ° C for 24 hours, then treated with HCl (10%) and extracted with 40 ml of ethyl acetate, the organic phase is washed with water (2 x 30 ml) then dried over Na ₂ SO ₉ . Finally the product is purified by column chromatography (silica 8 hexane / 2 Chloroform).

EXAMPLE 24A compound 1.24

0.24 g of 2-iodo-5- (phenylethynyl) thiophene are suspended in 20 ml of oxygen-free triethylamine. To this suspension 30 mg of dichlorobistriphenylphosphine palladium (II), 0.004 g of copper iodide and 0.125 g of 5.1 l, 17,23-tetraethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 1.22) are added. The reaction mixture is heated at 40 ° C for 24 hours, then treated with HCl (10%) and extracted with 40 ml of ethyl acetate, the organic phase is washed with water (2 x 30 ml) then dried over Na ₂ SO ₄ . Finally the product is purified by column chromatography (8: hexane / 2 CHC1 ₃ ).

An analogous compound was also prepared from compound 1.22 and 2-iodo 5 - [(4-pentylphenyl) ethynyl] thiophene

B - COMPLEXES (II)

EXAMPLES IB

Complex of compound 1.6 with AgSO ₃ CF ₃ : Ag ₄ [I.6] ⁴⁺ compound II.l 0.1 g of compound 1.6 are dissolved in 10 ml of chloroform. 0.1 g of AgSO ₃ CF ₃ are added to the solution and the reaction mixture is stirred for about 12 hours at room temperature and protected from light. After filtration, the red powder obtained is washed with methanol and diethyl ether. Elementary microanalysis: Ag ₄ [L6] (SO ₃ CF ₃ ) ₄ , C ₅ H ₅ N

Found: C 34.07% N 6.20% H 1.82% S 12.49% Ag 22.41% Calculated: C 33.98% N 6.24% H 1.83% S 12.68% Ag 21.37%.

EXAMPLE 2B Complex of compound 1.6 with ZnCl ₂ : Zn [I.6] ₂ ²⁺ compound II.2

0.1 g of compound 1.6 are dissolved in a 10/1 (v / v) chloroform / tetrahydrofuran mixture. To this orange-colored solution, 0.1 g of zinc (II) chloride and 0.2 ml of pyridine are added. The solution is stirred for 48 hours at room temperature. The yellow suspension is filtered. The yellow powder obtained is washed with water, methanol and diethyl ether. Elementary microanalysis: Zn [I.6] ₂ Cl ₂ , C ₅ H ₅ N Found: C 57.06% N 11.29% H 3.39% S 11.94% Zn 3.57% Calculated: C 60, 00% N 11.89% H 3.49% S 12.00% Zn 3.08%.

EXAMPLE 3B

Complex of compound 1.6 with CuCl ₂ : Cu [1.6] ⁴⁺ compound II.3

0.1 g of compound 1.6 are dissolved in 10 ml of chloroform. 0.063 g of copper (II) chloride are added to this solution. The suspension is stirred for 24 hours at room temperature. The suspension is filtered, then the solvents are evaporated. The brown powder is washed with methanol, water and diethyl ether.

Elementary microanalysis: Cu ₄ [I.6] Cl ₈ , C ₅ H ₅ N Found: C 43.87% N 7.86% H 2.90% S 8.71% Cu 16.77% Calculated: C 41, 50% N 8.20% H 2.41% S 8.36% Cu 16.61%.

EXAMPLE 4B

Complex of compound 1.7 with AgSO ₃ CF ₃ : Ag ₅ [I.7] ₂ ⁵⁺ compound II.4 0.15 g of compound 1.7 are dissolved in 20 ml of pyridine. 0.1 g of AgSO ₃ CF ₃ are added and the reaction mixture is stirred for 24 hours at room temperature and protected from light. Precipitation is carried out with methanol, the purple powder obtained is washed with methanol and with diethyl ether. Elementary microanalysis: Ag ₅ [IJ] ₂ (SO ₃ CF ₃ ) ₅ , 13C ₅ H ₅ N

Found: C 46.07% N 12.62% H 2.38% S 9.22% Ag 12.14% Calculated: C 44.30% N 11.52% H 2.69% S 9.25% Ag 11.99%.

EXAMPLE 5B Complex of compound 1.7 with ZnCI ₂ : Zn [I.7] ₂ ⁺² compound II.5

0.1 g of compound 1.7 are suspended in 10 ml of tetrahydrofuran. To this suspension, 0.1 g of zinc (II) chloride and 0.9 ml of water are added. The suspension is stirred for 69 hours at room temperature. The suspension is filtered. The filtrate is concentrated and then precipitated with methanol. The purple powder obtained is washed with methanol, water and diethyl ether. Elementary microanalysis: Zn [IJ] ₂ Cl ₂ Found: C 48.09% N 12.63% H 2.68% S 9.14% Zn 3.29% Calculated: C 49.60% N 14.47% H 2.41% S 11.00% Zn 2.81%.

The differences obtained between the calculated and experimental elementary microanalysis results can be attributed to the presence of solvation molecules.

EXAMPLE 6B

Platinum complex with compound 1.22: compound II.6 of formula:

with R = n-propyl

0.1 g of Trans- [PtCl (PEt ₃ ) ₂ (C≡C-phenyl)] is dissolved in a mixture of 1 toluene / 1 diethylamine. To this solution is added 0.003 g of cuprous chloride and then a solution of 0.028 g of 5, ll, 17.23-Tetraethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 22.1) in 10 ml of toluene. The reaction mixture is stirred at room temperature for 24 hours, evaporated to dryness and then taken up in dichloromethane. The organic phase is dried over magnesium sulphate then evaporated to dryness The residue is purified by chromatography on basic alumina. A complex analogous to compound II.6, with Trans- {PtCl (PEt ₃ ) ₂ [C≡C- (4-pentylphenyl)]} was also prepared according to the same procedure.

Complexes analogous to compound II.6, in which R = methyl or -C ₂ H ₄ O ₂ CNHC ₂ H ₄ Si (OEt) ₃ , were also prepared according to the same procedure. EXAMPLE 7B

Platinum complex with compound 1.25: compound II.7 of formula

with R = n-propyl This complex is prepared according to the same procedure as that of EXAMPLE 6B.

A complex analogous to compound IIJ, with Trans- {PtCl (PEt ₃ ) ₂ [C≡C- (4-pentylphenyl)]} was also prepared according to the same procedure. Complexes analogous to compound IIJ, in which R = methyl or -C ₂ H ₄ O ₂ CNHC ₂ H ₄ Si (OEt) ₃ , were also prepared according to the same procedure.

Claims

1 - Metal complexes (II) with a thiacalix [4] arene, optionally in the form of a salt, solvate or hydrate, of formula (I):

in which :

- R _la , R _2a , R _3a and R _a , identical or different, each independently represent:

- a hydrogen atom,

- an (Cι.-C ₁₂ ) alkyl group,

- a (Cι-C ₁₂ ) alkenyl group,

- a group -SO ₂ -Rι_, in which Ri _. represents a phenyl, benzyl or naphthyl group, unsubstituted or substituted one or more times by a halogen atom, a (C ₁ -C ₄ ) alkyl, (Cι _. -C ₄ ) alkenyl or (Cι.-C ₄ ) alkynyl, or else,

- A group -SiR ₂ R ₃ R ₄ , in which R ₂ , R ₃ and R ₄ each independently represent a (Cι _. -C ₄ ) alkyl group;

- Rîb, R2b, R3b and R ₄ , identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom,

- an (Cι-C ₆ ) alkyl group,

- a group -N = CHR ₅ in which R ₅ represents a (Cι.-C) alkyl, pyridyl or phenyl group,

- a group -C≡CR ₆ in which Rβ represents a hydrogen atom, an (Cι-C ₄ ) alkyl, tri (Cι-C) alkylsilyl or phenyl group,

- a nitro group, or,

- a group -NR R ₈ , in which R represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (Cι _. -C ₄ ) alkyl, pyridyl or phenyl, it being understood that when at least one of _the groups R, R 2a, R 3a and R _4a represents a methyl group, the other representing a hydrogen atom, or when R _a = R 2a = R 3a = i _a and represent either a (C ₂ -C ₄ ) alkyl group or a hydrogen atom, then at least one of the substituents Rib, R2b, 3b or R ₄ is different from hydrogen or from the group tert-butyl.

2 - Metallic complexes (II) with a thiacalix [4] arene, optionally in the form of a salt, solvate or hydrate, of formula (I):

in which :

- R _la , R _2a , R3a and R _4a , identical or different, each independently represent:

- a hydrogen atom,

- an (Cι-Cι) alkyl group,

- a (Cι-Cι ₂ ) alkenyl group,

- a group -SO ₂ -Rι, in which Ri. represents a phenyl, benzyl or naphthyl group, unsubstituted or substituted one or more times by a halogen atom, a (Cι.-C ₄ ) alkyl, (Cι _. -C ₄ ) alkenyl or (Cι.-C ₄ ) alkynyl, or else,

- A group -SiR ₂ R3R ₄ , in which R ₂ , R ₃ and R ₄ each independently represent a (Cι.-C ₄ ) alkyl group; - Rι _. , R _2b , R3b and Rjb, identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom, - a (Cι-C ₆ ) alkyl group,

- a group -N = CHR ₅ in which R ₅ represents a (Cι-C ₄ ) alkyl, pyridyl or phenyl group, - a group -G≡CR ₆ in which R ₆ represents a hydrogen atom, a group tri (Cι-C ₄ ) alkylsilyl, phenyl, or a group of formula:

where R _Ô 'represents a hydrogen atom or a phenyl optionally substituted in para by a group (-C ^ alkyl,

- a nitro group or,

- a group -NR R ₈ , in which R represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (-C ^ alkyl, pyridyl or phenyl, it being understood that when at least one of _the groups R, R _2a, R 3a and R _4a represents a methyl group, the other representing a hydrogen atom, or when R _a = R _2a = ₃ has = _4a and represent either a (C ₂ -C ₄ ) alkyl group or a hydrogen atom, then at least one of the substituents R ^, R2b, ₃ or R _4b is different from hydrogen or from the group 3-Metallic complexes (II) according to claim 1, characterized in that:

- R _la , R _2a , R _3a and _ta , identical or different, each independently represent:

- a hydrogen atom,

- a (Cι-Cι ₂ ) alkyl group, - a (Cι-Cι ₂ ) alkenyl group, or

- a group -S1R ₂ R _{5 1} , in which R ₂ , R ₃ and R). each independently represent a (Cι-C ₄ ) alkyl group; - R ^, R _2b , R _3b and Rtb, identical or different, each independently represent:

- a hydrogen atom,

- a halogen atom, - a (-C ^ alkyl) group,

a group -N = CHR in which R ₅ represents a group (Cι _. -C ₄ ) alkyl, pyridyl or phenyl,

a group -C≡CR _Ô in which Rg represents a hydrogen atom, a (Cι_-C ₄ ) alkyl, tri (Cι-C ₄ ) alkylsilyl or phenyl group, - a nitro group, or alternatively,

- a group -N = CR ₅ or -NR ₇ R ₈ , in which R represents a hydrogen atom and R ₈ represents a hydrogen atom or a group

-C (O) R ₅ where R is selected from a (Cι-C ₄₎ alkyl, pyridyl or phenyl, it being understood that when at least one of _the groups R, R _2a, R 3a and R _4a represents a group methyl, the others representing a hydrogen atom, or else when Rι _a = R _a = R _3a - _t a and represent either a (C -C ₄ ) alkyl group or a hydrogen atom, then one at least one of the substituents R 1, R ₂ b, R ₃ b or j _b is different from hydrogen or from the tert-butyl group. 4 - Metal complexes (II) according to claim 2, characterized in that:

- R _la , R _a , R ₃ a and R ^, identical or different, each independently represent:

- a hydrogen atom,

- a (C ₁ -Cι ₂ ) alkyl group, - a (C ₁ -C ₁₂ ) alkenyl group, or else,

- A group -SiR ^ R- _t , in which R ₂ , R ₃ and R ₄ each independently represent a (Cι-C ₄ ) alkyl group;

- Ri, R _2b , R _3b and R ^, identical or different, each independently represent: - a hydrogen atom,

- a halogen atom,

- an (Cι-C ₆ ) alkyl group,

- a group -N = CHR ₅ in which R ₅ represents a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, a group -C≡CR _Ô in which R _ό represents a hydrogen atom, a group (Cι-C ₄ ) alkyl, tri (Cι-C ₄ ) alkylsilyl phenyl, or a group of formula:

C≡CR _β

W // where R _ό 'represents a hydrogen atom or a phenyl optionally substituted in para by a (Cι-C ₆ ) alkyl group, - a nitro group or else,

- a group -NR ₇ R ₈ , in which R ₇ represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with

R ₅ chosen from a (Cι-C ₄ ) alkyl, pyridyl or phenyl group, it being understood that, when at least one of the groups Rι _a , R _2a , R _a or R _4a represents a methyl group, the others representing a hydrogen atom, or when Rι _a = R _2a = R ₃ a = _ta and represent either a (C ₂ -C ₄ ) alkyl group or a hydrogen atom, then at least one of the Rib substituents , R2b, R3b or R ₄ b is different from hydrogen or the tert-butyl group.

5 - Metal complexes (II) according to one of claims 1 to 4 characterized in that at least one of the substituents Ri, R ₂ b, R _3b or R <tb represents a nitro group, -N = CHR ₅ or -NR ₇ R ₈ , in which R represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (Cι-C ₄ ) alkyl, pyridyl or phenyl.

6 - Metal complexes (II) according to one of claims 1 to 6 characterized in that the thiacalix [4] arene is of formula (la):

in which Rι _a , R _2a , Ri and R ₂ are as defined in claims 1 to 5.

7 - Metal complexes (II) according to claim 6 characterized in that Rι _a represents a hydrogen atom or a (Cι-Cι ₂ ) alkyl or (Cι-Cι ₂ ) alkenyl and R _2a represents a hydrogen atom or a group (Cι-C ₁₂ ) alkyl, (Cι-Cι ₂ ) alkenyl, - SO ₂ -Rι or -SiR ₂ RR ₄ ; Ri, R ₂ , R ₃ and R ₄ being as defined for (I) in claim 1 or 2.

8 - Metal complexes (II) according to one of claims 1 to 7 characterized in that the thiacalix [4] arene is of formula (Ib):

in which Rι _a , R _2a and Ri _b are as defined in claims 1 to 7. 9 - Metal complexes (II) according to one of claims 1 to 8 characterized in that the thiacalix [4] arene is of formula ( the) :

in which Rι _a and Ri are as defined in claims 1 to 8. 10 - Metal complexes (II) according to claims 1 characterized in that the thiacalix [4] arene is chosen from:

- 5,11,17,23-Tétraiodo-25,26,27,28-tétrahydroxythiacalix [4] arène, - 5, ll, 17,23-Tétrabromo-25,26,27,28-tétrahydroxythiacalix [4] arène, -5,11,17,23-tetra (tert-butyl) -25-propoxy-26,27,28-trihydroxythiacalix [4] arena,

-5.1 l, 17.23-Tetra (tert-butyl) -25.27-di (tert-butyldimethylsiloxy) -26.28-di-hydroxythiacalix [4] arene,

- 5, ll, 17,23-Tetra (tert-butyl) -25,26,27,28-tetrahexyloxythiacalix [4] arene, - 5,11,17,23-Tetrakis (phenylazo) -25,26,27, 28-tétrahydroxythiacalix [4] arena

-5, ll, 17.23-Tetrakis (4-nitrophenylazo) -25,26,27,28-tetrahydroxythiacalix [4] arene, -5, ll, 17,23-Tetra (tert-butyl) -25, 27-di (4-toluenesulfonyloxy) -26,28-di-hydroxythiacalix [4] arene, - 5.1 l, 17.23-Tetranitro-25,26,27,28-tetrahydroxythiacalix [4] arene,

- 5.1 l tetrachlorhydrate, 17,23-tetraamino-25,26,27,28-tetrahydroxythiacalix [4] arene,

- 25.27-Di (4-toluenesulfonyloxy) -26.28-dihydroxythiacalix [4] arene,

- 25, 27-Di (tert-butyldimethylsiloxy) -26,28-dihy droxythiacalix [4] arene, -5, ll, 17,23-Tetrakis (phenylazo) -25,27-di (4-toluenesulfonyloxy) -26, 28-di- hydroxythiacalix [4] arena,

- 5,11,17,23 -Tetrakis (4-nitrophenylazo) -25,27-di (4-toluènesulfonyloxy) - 26,28-dihydroxythiacalix [4] arene,

- 5,17-Diiodo-25,26,27,28-tetrahydroxythiacalix [4] arene, - 5,17-Dibromo-25,26,27,28-tetrahydroxythiacalix [4] arene,

- 5.1 l, 17.23-Tetra (phenylethynyl) -25,26,27,28-tetrahydroxythiacalix [4] arene, - 5, ll, 17,23-Tetraethynyl-25,26,27,28- tetrahydroxythiacalix [4] arena.

11 - Metal complexes (II) according to one of claims 1 to 10 with a transition metal.

12 - Metal complexes (II) according to claim 11 with copper, silver, zinc, lead or platinum.

13 - Metal complexes (II) according to claim 12 with copper, zinc or nickel. 14 - Use of a thiacali [4] arene (I) or a metal complex (II) as defined in one of claims 1 to 13 for the manufacture of materials having properties of optical limiters.

15 - Use according to claim 14 for the manufacture of protective materials against lasers.

16 - Use of a metal complex (II) as defined in claim 13 for the manufacture of thermochromic materials.

17 - Process for the preparation of a thiacalix [4] arene of formula (I) as defined in claim 5 in which at least one of the substituents Rib, R2b, R3b or R ₄ b represents a nitro group, -N ≈CHRs or -NRγRs, in which R represents a hydrogen atom and R ₈ represents a hydrogen atom or a group -C (O) R ₅ with R ₅ chosen from a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, characterized in that: a) if Ri, R2b, R3b and / or R ^ represent a nitro group, the compound (I) is obtained by nitration of the corresponding thiacalix [4] arene in which the (s) says ( s) group (s) Rib, R ₂ b, 3b and / or P% b represent a hydrogen atom, by the action of nitrogen dioxide or nitrogen tetroxide in the presence of an ethereal solvent; b) if Ri, R2b, R3b and / or P% represent an amino group, the compound (I) is obtained by reduction of the corresponding compound (I) in which the said group (s) Rib (s), R2b , R3b and / or R ^ represent a nitro group; c) if Rib, R ₂ b, R3b and / or R4b represent a group -N = CHR ₅ , R ₅ representing a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, the compound (I) is prepared from corresponding compound (I) in which the said group (s) Rib, R2b, R3b and / or R ₄ b represent an amino group, by the action of an aldehyde R ₅ -CHO, or of a ketone R ₅ -C (O) R ₉ , R ₅ and R ₉ , identical or different, representing independently of one another, a (dC ₄ ) alkyl, pyridyl or phenyl group; d) if Rib, R2b, 3b and / or R ^ represent a group -NHC (O) R ₅ in which R ₅ represents a group (Cι-C ₄ ) alkyl, pyridyl or phenyl, the compound (I) is obtained from the corresponding compound (I) in which Rib, R2b, R3 and / or ib represent an amino group by the action of the acid halide Hal-C (O) R ₅ in which Hal is a halogen atom and R ₅ is as defined above.

18 - Process according to claim 17, characterized in that in paragraph a), nitrogen dioxide or nitrogen tetroxide is formed in situ in the presence of aluminum trichloride and potassium nitrate. 19 - Process according to claim 17 or 18, characterized in that in paragraph a), the nitrogen dioxide or nitrogen tetroxide is in the form of a complex with the ethereal solvent.

20 - Method according to one of claims 17 to 19, characterized in that in paragraph a), is used as ether solvent diglyme, triglyme, tetraglyme or a crown ether.