Method for Producing Branched Oligoarylsilanes

Abstract

Branched oligoarylsilanes of general formula (I)

X.sub.mQ.sub.k-SiAr.sub.n—R).sub.3].sub.2  (I).

A method of preparation of branched oligoarylsilanes is that a compound of general formula (III)

Y-Q.sub.k-SiAr.sub.n—R).sub.3  (III),

where Y stands for a residue of boronic acid or its ester or Br or I, reacts under Suzuki conditions with a reagent of general formula (IV)

A-X.sub.m-A  (IV),

where A stands for: Br or I, provided that Y stands for a residue of boronic acid or its ester; or a residue of boronic acid or its ester, provided that Y stands for Br or I. A technical result is preparation of novel compounds, featured by a high luminescence efficiency, efficient intramolecular energy transfer from some molecular fragments to others, and an increased thermal stability.

Claims

1. A method of preparation of branched oligoarylsilanes of formula (I),
X.sub.mQ.sub.k-SiAr.sub.n—R).sub.3].sub.2  (I) where R stands for a substituent from a group including: linear or branched C.sub.1-C.sub.20 alkyl groups; linear or branched C.sub.1-C.sub.20 alkyl groups, separated by at least one oxygen atom; linear or branched C.sub.1-C.sub.20 alkyl groups, separated by at least one sulfur atom; branched C.sub.3-C.sub.20 alkyl groups, separated by at least one silicon atom; C.sub.2-C.sub.20 alkenyl groups, Ar stands for identical or different arylene or hetetoarylene radicals, selected from a group including: substituted or unsubstituted thienyl-2,5-diyl of formula (II-a) ##STR00033## substituted or unsubstituted phenyl-1,4-diyl of formula (II-b) ##STR00034## substituted or unsubstituted 1,3-oxazole-2,5-diyl of formula (II-c) ##STR00035## substituted fluorene-4,4′-diyl of formula (II-d) ##STR00036## substituted cyclopentathiophene-2,7-diyl of formula (II-e) ##STR00037## where R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, independently on each other stand for H or a substituent from the aforementioned group for R; R.sub.6, R.sub.7, R.sub.8, R.sub.9 stands for a substituent from the aforementioned group for R, Q stands for a radical from the aforementioned group for Ar, X stands for at least one radical, selected from the aforementioned group for Ar and/or a radical from the group: 2,1,3-benzothiodiazole-4,7-diyl ##STR00038## of formula (II-f), antracene-9,10-diyl of formula (II-g) ##STR00039## 1,3,4-oxadiazole-2,5-diyl of formula (II-h) ##STR00040## 1-phenyl-2-pyrazoline-3,5-diyl of formula (II-i) ##STR00041## perylene-3,10-diyl of formula (II-j) ##STR00042## n stands for an integer from the group from 2 to 4, m stands for an integer from the group from 1 to 3, k stands for an integer from the group from 1 to 3, the method comprising: a compound of general formula (III)
Y-Q.sub.k-SiAr.sub.n—R).sub.3  (III) reacting under Suzuki conditions, where Y stands for a residue of boronic acid or its ester, or Br, or I, R, Ar, Q, n, k have the aforementioned values, with a reagent of general formula (IV)
A-X.sub.m-A  (IV), where A stands for: Br or I, if Y stands for a residue of boronic acid or its ester, or a residue of boronic acid or its ester, if Y stands for Br or I; and X and m have the aforementioned values.

2. The method according to claim 1, wherein a boronic ester is an ester, selected from a group including: 4,4,5,5-tetramethyl-1,3,2-dioxaborolane of general formula (V-a) ##STR00043## 1,3,2-dioxaborolane of general formula (V-b) ##STR00044## 1,2,3-dioxaborinane of general formula (V-c) ##STR00045## 5,5-dimethyl-1,2,3-dioxaborinane of general formula (V-d) ##STR00046##

3. The method according to claim 1, wherein A in the compound of formula (IV) stands for Br.

4. The method according to claim 1, wherein X stands for substituted fluorene-4,4′-diyl (II-d), under condition that Q stands for thienyl-2,5-diyl, selected from a number of compounds corresponding to the formulae (II-a), m is equal to 1, k is equal to 1.

5. The method according to claim 1, wherein X stands for phenyl-1,4-diyl (II-b) and 1,3-oxazole-2,5-diyl (II-c), under condition that Q stands for phenyl-1,4-diyl, selected from a number of compounds corresponding to the formulae (II-c), m is equal to 3, k is equal to 1.

6. The method according to claim 1, wherein the reaction of components is carried out at temperatures ranging from 20 to 200° C., preferably at the temperature from 60 to 120° C.

7. The method according to claim 1, wherein the reaction of components is carried out in a medium of an organic solvent, selected from a group including toluene, tetrahydrofuran, ethanol, dioxane, dimethylformamide or their mixtures.

8. The method according to claim 1, wherein the branched oligoarylsilanes obtained possess a luminescence quantum yield of no less than 50%, predominantly no less than 70%.

9. The method according to claim 1, wherein the branched oligoarylsilanes obtained possess an intramolecular energy transfer efficiency of no less than 70%, predominantly no less than 90%.

10. The method according to claim 1, wherein the branched oligoarylsilanes obtained are thermally stable up to temperatures of no less than 200° C., preferably no less than 400° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In FIG. 1 a schematic representation of the novel branched oligoarylsilanes is shown.

[0019] In FIG. 2 a schematic representation of the compounds of general formula (III) is shown.

[0020] In FIG. 3 a schematic representation of the structural formulae of the novel branched oligoarylsilane I-1 (according to example 4) is shown.

[0021] In FIG. 4 absorption (a) and luminescence (b) spectra of the novel branched oligoarylsilane I-1 in diluted THF (tetrahydrofurane) solution are shown.

[0022] In FIG. 5 a GPC curve of pure compound I-1 is shown.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] A schematic representation of the novel branched oligoarylsilanes is depicted in FIG. 1, where the tinted oval stands for the inner part of the molecule, and the non-tinted ovals—for the outer luminophores. The preferred examples for R are linear or branched C.sub.1-C.sub.20 alkyl groups, for instance, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, iso-butyl, sec-butyl, n-penthyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl. The most preferred examples for R are: methyl, ethyl, n-hexyl, 2-ethylhexyl.

[0024] The preferred examples of Ar are: unsubstituted thienyl-2,5-diyl of general formula (II-a), where R.sub.1═R.sub.2═H; substituted thienyl-2,5-diyl of general formula (II-a), where R.sub.1═H, in particular, 3-methylthienyl-2,5-diyl, 3-ethylthienyl-2,5-diyl, 3-propylthienyl-2,5-diyl, 3-butylthienyl-2,5-diyl, 3-penthylthienyl-2,5-diyl, 3-hexylthienyl-2,5-diyl, 3-(2-ethylhexyl)thienyl-2,5-diyl; unsubstituted phenyl-1,4-diyl of general formula (II-b), where R.sub.3═R.sub.4═H; substituted phenyl-1,4-diyl of general formula (II-b), where R.sub.3═H, in particular, (2,5-dimethyl)phenyl-1,4-diyl, (2,5-diethyl)phenyl-1,4-diyl, (2,5-dipropyl)phenyl-1,4-diyl, (2,5-dibutyl)phenyl-1,4-diyl, (2,5-dipenthyl)phenyl-1,4-diyl, (2,5-dihexyl)phenyl-1,4-diyl, 2,5-bis(2-ethylhexyl) phenyl-1,4-diyl, (2,5-dimethoxy)phenyl-1,4-diyl, (2,5-diethoxy)phenyl-1,4-diyl, (2,5-dipropoxy)phenyl-1,4-diyl, (2,5-diisoprooxy)phenyl-1,4-diyl, (2,5-dibutoxy)phenyl-1,4-diyl, (2,5-dipenthyloxy)phenyl-1,4-diyl, (2,5-dihexyloxy)phenyl-1,4-diyl, 2,5-bis(2-ethylhexyloxy)phenyl-1,4-diyl. The preferred examples of Ar: thienyl-2,5-diyl, phenyl-1,4-diyl and (2,5-dimethyl)phenyl-1,4-diyl.

[0025] In the context of the present invention Ar.sub.n refers to any combination of n fragments of identical or different Ar, selected from the row described above. The preferred values of such combination are n identical unsubstituted thienyl-2,5-diyl fragment, linked to each other in the positions 2 and 5, for instance, 2,2′-bithienyl-2,5′-diyl (II-a-1), 2,2′:5′,2″-terthienyl-2,5″-diyl (II-a-2):

##STR00014##

[0026] The other preferred value of such combination is a sequence of different unsubstituted or 2,5-substituted phenyl fragments, linked to each other in the positions 1 or 4, and different unsubstituted 1,3-oxazole-2,5-diyl fragments in such a way that their overall number is equal to n, for instance, when n=2 formula (II-1), when n=3 any of the formulas (II-2)-(II-4):

##STR00015##

[0027] In the context of the present invention Q.sub.k refers to any combination of k fragments of identical or different Q, selected from the row described above. The preferred values of this combination are unsubstituted thienyl-2,5-diyl (II-a-3), unsubstituted phenyl-1,4-diyl (II-b-1), k identical unsubstituted thienyl-2,5-diyl fragments, linked to each other in the position 2 and 5, for instance, 2,2′-bithienyl-2,5′-diyl (II-b-1), 2,2′:5′,2″-terthienyl-2,5″-diyl (II-a-2):

##STR00016##

[0028] In the context of the present invention X.sub.m refers to any combination of m fragments of identical or different X, selected from the row described above. The preferred values of such fragments are unsubstituted phenyl-1,4-diyl (II-b-1), unsubstituted 1,3-oxazole-2,5-diyl, unsubstituted thienyl-2,5-diyl (II-a-3), antracene-9,10-diyl (II-e), 1,3,4-oxadiazole-2,5-diyl (II-f), 2,1,3-benzothiadiazole-4,7-diyl.

[0029] In the context of the present invention X.sub.m(Q.sub.k).sub.2 refers to any combination of m fragments of identical or different X and k fragments of identical or different Q, selected from the rows described above. The preferred examples of the combinations of these fragments are: 2,1,3-benzothiodiazole-4,7-diylbis(thien-2,5-diyl) (II-5), 2,1,3-benzothiodiazole-4,7-diylbis(2,2′-bithien-5′,5-diyl) (II-6), antracene-9,10-diylbis(phenylene-1,4-diyl) (II-7), antracene-9,10-diylbis(thien-2,5-diyl) (II-8), 2,2′-[1,4-phenylene]bis(1,3-oxazole-2,5-diyl-phenylene-4,1-diyl) (II-9), substituted fluorene-4,4′-diylbis(thien-2,5-diyl) (II-10):

##STR00017##

[0030] The positions, marked in the formulas (II-a-1)-(II-a-3) and (II-1)-(II-9) with a sign * (star) are the points in the molecules, in which the structural fragments (II-a)-(II-h) are linked to each other in the form of linear conjugated oligomer chains Ar.sub.n, X.sub.m, Q.sub.k or the ends of the chains Ar.sub.n or X.sub.m(Q.sub.k).sub.2, linked with silicon atoms in the points of branching or the terminal substituents R and R.sub.1.

[0031] The described values for R, Ar, Ar.sub.n, Q, Q.sub.k, X, X.sub.m are particular cases and do not limit all possible combinations of n, m, k for the values of Ar, Q, X between them.

[0032] In particular, in the formula (I) Ar may stand for thienyl-2,5-diyl, selected from a number of the compounds of the formula (II-a), then the general formula has a following structure:

##STR00018##

where X, Q, R, R.sub.1, R.sub.2, n, m, k have the values described above.

[0033] In particular, in the formula (I) Ar may stand for phenyl-1,4-diyl, selected from a number of compounds with the formula (II-b), then the general formula has the following structure:

##STR00019##

where X, Q, R, R.sub.3, R.sub.4, n, m, k have the values described above.

[0034] In particular, in the formula (I) X may stand for substituted fluorene-4,4′-diyl (II-d), when Q stands for thienyl-2,5-diyl, selected from a number of compounds with the formula (II-a), m is equal to 1, k is equal to 1, then the general formula has the following structure:

##STR00020##

where Ar, R, R.sub.6, R.sub.7 and n have the values described above.

[0035] In this case, for instance, when Ar=unsubstituted thienyl-2,5-diyl, R═C.sub.6H.sub.13, R.sub.6═R.sub.7═C.sub.10H.sub.21, n=2, the novel branched oligoarylsilane (FIG. 3) may be described by the formula (I-1):

##STR00021##

[0036] In particular, in the formula (I) X may stand for phenyl-1,4-diyl (II-b) and 1,3-oxazole-2,5-diyl (II-c), when Q stands for phenyl-1,4-diyl, selected from a number of compounds with the formula (II-b), m is equal to 3, k is equal to 1, then the general formula has the following structure:

##STR00022##

where Ar, R, R.sub.3, R.sub.4, R.sub.5 and n have the values described above.

[0037] In particular, in the formula (I) n may be is equal to 2, then the general formula has the following structure:

X.sub.mQ.sub.k-SiAr.sub.2—R).sub.3].sub.2  (I-e)

where R, Ar, X, Q, k and m have the values described above.

[0038] In particular, in the formula (I) n may be is equal to 3, then the general formula has the following structure:

X.sub.mQ.sub.k-SiAr.sub.3—R).sub.3].sub.2  (I-f)

where R, Ar, X, Q, k and m have the values described above.

[0039] The novel branched oligoarylsilanes claimed contain identical or different aryl- or heteroarylsilane groups, which exhibit efficient luminescence. This may be illustrated by the absorption and luminescence spectra of their dilute solutions (see, for instance, FIG. 4). As can be seen from the spectral data, the novel branched oligoarylsilanes claimed possess a wide absorption spectrum with two characteristic maxima, a high luminescence quantum yield and efficient intramolecular energy transfer. A high quantum yield in the present invention refers to a luminescence quantum yield in dilute solution equal to or above 50%, preferably exceeding 70%. An efficient intramolecular energy transfer refers to an efficiency of no less than 70%, preferably no less than 90%. The data described gives only some examples of the claimed branched oligoarylsilanes, and does not limit their potential properties at all.

[0040] A characteristic feature of the oligoarylsilanes claimed is their high thermal stability, defined within the present invention as the temperature of 1% weight loss during the compound heating under argon atmosphere. This temperature for different particular cases is no less than 200° C., preferably no less than 400° C.

[0041] A solution is also provided by elaborated method of synthesis of novel branched oligoarylsilanes of general formula (I). This method can be briefly described as follows. A compound of general formula (III)

Y-Q.sub.k-SiAr.sub.n—R).sub.3  (III)

[0042] where Y stands for the residue of boric acid or its ester, or Br, or I,

[0043] R, Ar, Q, n, k have the values pointed above,

[0044] react under Suzuki conditions with a reagent of general formula (IV)

A-X.sub.m-A  (IV),

[0045] where A stands for Br or I, provided that Y stands for the residue of boric acid or its

[0046] ester, or for the residue of boric acid or its ester, provided that Y stands for Br or I.

X, m have the values pointed above.

[0047] Under Suzuki reaction we understand a reaction of aryl- or heteroaryl-halogenide with aryl- or heteroaryl-organoboronic compound (Suzuki, Chem. Rev. 1995. V.95. P.2457-2483) in the presence of a base and a catalyst, containing metal of the VIII subgroup of periodic table. It's well known that for this reaction any available base can be used, such as hydroxides, for instance, NaOH, KOH, LiOH, Ba(OH).sub.2, Ca(OH).sub.2; alkoxides, for instance, NaOEt, KOEt, LiOEt, NaOMe, KOMe, LiOMe; alkali metal salts of carbonic acids, for instance, carbonates, hydrocarbonates, acetates, cytrates, acetylacetonates, sodium, potassium or lithium glicinates, for instance, Cs.sub.2CO.sub.3, Tl.sub.2CO.sub.3; phosphates, for instance, sodium, potassium or lithium phosphates. The preferred base is sodium carbonate. Bases are used in the form of water solutions or suspensions in organic solvents, such as toluene, dioxane, ethanole, dimethylformamide or their mixtures. Water-based solutions are preferred. Also any compounds, containing metals of VIII subgroup of Periodic table may be used as the catalysts in Suzuki reaction. The preferred metals are Pd, Ni, Pt. The most preferred metal is Pd. Catalyst or catalysts preferably are used in the amounts ranging from 0.01 mol % to 10 mol %. The most preferable amount of the catalyst is between 0.5 mol % and 5 mol % in respect to the molar amount of the reagent with the lower molar mass. The most available catalysts are complexes of VIII subgroup metals. In particular, stable in air conditions palladium (0) complexes, palladium complexes, which are reduces directly in the reaction vessel by organometallic compounds (alkyllithium or organomagnesium compounds) or phosphines to palladium (0), such as palladium(II) complexes with triphenylphosphine or other phosphines. For instance, PdCl.sub.2(PPh.sub.3).sub.2, PdBr.sub.2(PPh.sub.3).sub.2, Pd(OAc).sub.2 or their mixtures with triphenylphosphine. It is preferable to use commercially available Pd(PPh.sub.3).sub.4 with or without additionally added phosphines. As phosphines it is preferable to use PPh.sub.3, PEtPh.sub.2, PMePh.sub.2, PEt.sub.2Ph, PEt.sub.3. The most preferable is triphenylphosphine.

[0048] A general scheme of the process may be depicted as following:

##STR00023##

[0049] where A, X, Y, Q, Ar, R, n, m and k have the values pointed above.

[0050] In particular, Y for a compound of formula (III) may stand for the residue of the cyclic ester of boronic acid—4,4,5,5-tetramethyl-1,3,2-dioxaborolane of general formula (V)

##STR00024##

in this case a branched oligoarylsilane is obtained according to the following general scheme:

##STR00025##

where A, X, Q, Ar, R, n, m, and k have the values pointed above.

[0051] In particular, for a compound of formula (IV) A may stand for Br, then a branched oligoarylsilane is obtained according to the following general scheme:

##STR00026##

[0052] where X, Y, Q, Ar, R, R.sub.1, n, m and k have the values pointed above.

[0053] In particular, for a compound of formula (IV) X may stand for substituted fluorene-4,4′-diyl (II-d), under condition that Q stands for thienyl-2,5-diyl, selected from a number of compounds of formula (II-a), m is equal to 1, k is equal to 1, then the branched oligoarylsilane is obtained according to the following general scheme:

##STR00027##

where A, Y, Ar, R, R.sub.6, R.sub.7, n have the values pointed above.

[0054] In particular, for a compound of formula (IV) X may stand for phenyl-1,4-diyl (II-b) and 1,3-oxazole-2,5-diyl(II-c), under condition that Q stands for phenyl-1,4-diyl, selected from a number of compounds of formula (II-b), m is equal to 3, k is equal to 1, then the branched oligoarylsilane is obtained according to the following general scheme:

##STR00028##

where A, Y, Ar, R, R.sub.3, R.sub.4, R.sub.5, n have the values pointed above.

[0055] The reactions described above may be carried out in organic solvents or mixtures of solvent which do not interact with the reacting species. For instance, a reaction can be carried out in a medium of an organic solvent, selected from a number of ethers: tetrahydrofurane, dioxane, dimethyl ether of ethylene glycol, diethyl ether of ethylene glycol, dimethyl ether of ethylene glycol; otherwise, from a number of aromatic compounds: benzene, toluene, xylene, or from a number of alkanes: pentane, hexane, heptane, or from a number of alcohols: methanol, ethanol, isopropanol, butanol, or from the row aprotic polar solvents: dimethyl formamide, dimethyl sulfoxide. A mixture of two or more solvents may be used as well. The most preferred solvents are toluene, tetrahydrofurane, ethanol, dimethyl formamide or their mixtures. In these cases the initial components may react at temperatures ranging from +20° C. to +200° C. under a stoichiometric molar ratio between functional groups of the initial components or an excess of one of them. The reaction is preferably conducted at temperatures ranging from +40° C. to +150° C. The most preferred temperature region for the reaction is between +60° C. and +120° C.

[0056] After completion of the reaction, the product is isolated according to the known methods. For instance, water and an organic solvent are added. The organic phase is separated, washed with water until the pH is neutral and dried, after that the solvent is evaporated. As an organic solvent any immiscible or limitedly miscible with water solvent may be used, for instance, selected from a number of ethers: diethyl ether, methyltertbutyl ether, or selected from a number of aromatic compounds: benzene, toluene, xylene, or selected from a number of organochlorine compounds: dichloromethane, chloroform, carbon tetrachloride, chlorobenzene. Moreover, organic solvent mixtures may be used for the isolation. Isolation of the product may be performed also without organic solvents, for instance, via solvents evaporation from the reaction mixture, separation of the product from the water-based layer via filtration, centrifugation, or any other known method.

[0057] Purification of the raw product is performed by any known method, for instance, preparative chromatography in adsorption or exclusion regime, recrystallization, fractional precipitation or fractional dissolution, or any their combination.

[0058] Purity and molecular structure of the compounds synthesized is confirmed by a combination of physical and chemical analyses data well known for the skilled persons, such as chromatographic, spectroscopic, mass-spectroscopic, elemental analysis. The most preferred purity and molecular structure confirmation of novel branched oligoarylsilanes are .sup.1H, .sup.13C and .sup.29Si NMR-spectra, as well as GPC (gel permeation chromatography). GPC curves of a novel branched oligoarylsilane correspond to a narrow monodisperse molecular weight distribution (see, for instance, FIG. 5).

[0059] The invention may be illustrated by the following examples. Commercially available reagents and solvents were used. The initial reagent 5-hexyl-2,2′-bithiophene was prepared according to the known methods (S. Gronowitz, A.-B.-Hornfeldt, Thiophenes, Elsevier Academic press, 2004, pp. 755). Other initial compounds were prepared according to the following examples. All the reactions were carried out in anhydrous solvents under argon atmosphere.

Synthesis of the Starting Reagents

Example 1. Synthesis of 2-thienyltrimethoxysilane (VI)

[0060] ##STR00029##

[0061] To 27.73 ml (0.069 mol) of 2.5M solution of n-butyllithium in hexane at 0° C. 7.00 g (0.083 mol) of thiophene were added dropwise. The resulting lithium derivative of thiophene was added to 40 ml (0.166 mmol) tetraethoxysilane solution in 40 ml THF at 0° C. After vacuum distillation (T.sub.b=120° C./10 mbar) 7.07 g (34% from the theory) of compound VI were obtained. .sup.1H NMR (CDCl.sub.3): 1.27 (t, 9H, J=6.7 Hz), 3.90 (q, 6H, J.sub.1=6.7 Hz), 7.23 (dd, 1H, J.sub.1=3.7 Hz, J.sub.2=4.9 Hz), 7.50 (d, 1H, J=3.7 Hz), 7.67 (d, 1H, J=4.9 Hz).

Example 2. Synthesis of (2-thienyl)[tris(5′-hexyl-2,2′-bithienyl-5-yl)]silane (VII)

[0062] ##STR00030##

[0063] 5.28 ml (13 mmol) of 2.5M n-butyllithium solution in hexane were added to a solution of 3.3 g (13.2 mmol) of 5-hexyl-2,2′-bithiophene in 60 ml THF at −78° C. After that 1.03 g (0.42 mmol) of compound VI were added. In 30 minutes of stirring of the reaction mixture under cooling the reaction yield was 55% (according to GPC). After a standard isolation procedure and purification by means of column chromatography the chromatographically pure product yield was 1.59 g (44% from the theory). .sup.1H NMR (250 MHz, 6 in DMSO, TMS/ppm.): 0.89 (t, 9H, J=6.7 Hz), 1.25-1.45 (overlapping signals, 18H), 1.66 (m, 6H, M=5, J=6.7 Hz), 2.77 (t, 6H, J=7.3 Hz), 6.69 (dd, 3H, J.sub.1=3.7 Hz, J.sub.2=1.2 Hz), 7.03 (d, 3H, J=3.7 Hz), 7.23 (d, 3H, J=3.7 Hz), 7.29 (dd, 1H, J.sub.1=3.7 Hz, J.sub.2=4.3 Hz), 7.33 (d, 3H, J=3.7 Hz), 7.51 (d, 1H, J=3.7 Hz), 7.90 (d, 1H, J=4.3 Hz).

Example 3. Synthesis of tris(5′-hexyl-2,2′-bithien-5-yl)[5′-(4,4,5,5-tetramethyl-1,3,2-dioxyborolane-2-yl)-2,2′-bithien-5-yl]silane (III-1)

[0064] ##STR00031##

[0065] 1.1 ml (1.7 mmol) of 1.6M BuLi solution in hexane were added dropwise to a solution of 1.5 g (1.7 mmol) of compound VII in 40 ml THF, maintaining the temperature below −80° C. After that 0.36 ml (1.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxyborolane were added. The temperature was risen up to the room temperature, and 200 ml of distilled water, 300 ml of diethyl ether and 2 ml of 1N HCl water solution were added. After a standard isolation of the product, the yield of chromatographically pure product was 1.70 g (97% from the theory). .sup.1H NMR (δ in DMSO-CCl.sub.4, TMS/ppm.): 0.89 (9H, t, J=6.7 Hz), 1.23-1.41 (30H, overlapping peaks), 1.65 (6H, m, M=5, J=7.3), 2.77 (6H, t, J=7.3 Hz), 6.69 (3H, d, J=3.7 Hz), 7.05 (3H, d, J=3.7 Hz), 7.22 (3H, d, J=3.7 Hz), 7.33 (3H, d, J=3.7 Hz), 7.56 (1H, d, J=3.7 Hz), 7.67 (1H, t, J=3.7 Hz).

Synthesis of Novel Branched Oligoarylsilanes

[0066] A general method of the synthesis of branched oligoarylsilanes: 0.45 mmol of compound IV, 0.05 mmol catalyst, containing VIII subgroup of Periodic table metals, and 3.0 mmol base are added to a solution of 1.0 mmol of compound III in toluene. The mixture is stirred during several hours at 80° C.-120° C. After the reaction completion the product is isolated according to the known methods. The product is purified by means of column chromatography on silica gel.

Example 4. Synthesis of the Novel Branched Oligoarylsilane (I-1)

[0067] ##STR00032##

[0068] Branched oligoarylsilane I-1 was prepared according to the general synthetic method from 1.62 g of compound III-1, 0.45 g of 4,4′-dibromo-9,9-didecylfluorene, 0.095 g of the catalyst Pd(PPh.sub.3).sub.4, 3 ml of 2M Na.sub.2CO.sub.3 aqueous solution and 40 ml of toluene. After isolation and purification 0.549 g (35% from the theory) of pure branched oligoarylsilane (I-1) were obtained. .sup.1H NMR (δ in DMSO-CCl.sub.4, TMS/ppm.): 0.51-0.61 (overlapping signals, 4H), 0.78 (t, 6H, J=6.7 Hz), 0.89 (18H, t, J=6.7 Hz), 0.96-1.15 (overlapping signals, 28H), 1.23-1.41 (36H, overlapping peaks), 1.65 (12H, m, M=5, J=7.3), 1.96-2.03 (overlapping signals, 4H), 2.77 (12H, t, J=7.3 Hz), 6.69 (6H, d, J=3.7 Hz), 7.05 (6H, d, J=3.7 Hz), 7.25 (6H, d, J=3.7 Hz), 7.39 (6H, d, J=3.7 Hz), 7.47 (d, 2H, J=3.7 Hz), 7.58 (4H, s), 7.64 (2H, d, J=7.9 Hz), 7.73 (2H, d, J=7.9 Hz).

Examples 5-15. Synthesis of Novel Branched Oligoarylsilanes (I-2-I-12)

[0069] Synthesis of novel branched oligoarylsilanes I-2-I-12 was performed according to the general method from initial reagents under conditions described in Table 1. As a catalyst Pd(PPh.sub.3).sub.4 was used, while as a base—2M Na.sub.2CO.sub.3 aqueous solution similarly to example 4.

[0070] Although the best mode contemplated by the inventors of carrying out the present invention is disclosed above, practice of the above invention is not limited thereto. It will be manifest that various additions, modifications and rearrangements of the features of the present invention may be made without deviating from the spirit and the scope of the underlying inventive concept