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6,7-Dialkynyl-1,3-dimethylpteridine-2,4(1H,3H)-diones and 2,3-dialkynylquinoxalines have been shown to react with sodium azide in DMF at room temperature giving rise 9,11-dimethyl-[1,2,3]triazolo[1′,5′;1,2]pyrido[4,3-g]pteridine-8,10(9H,11H)-diones and [1,2,3]triazolo[1′,5′;1,2]pyrido[3,4-b]quinoxalines. A novel tandem cyclization involves 1,3-dipolar cycloaddition of an azide ion to the carbon–carbon triple bond followed by intramolecular nucleophilic addition of the intermediate 1,2,3-triazole N-anion to another C C bond.

The one-pot reaction of natural amino acids (glycine, β-alanine, γ-aminobutyric and ɛ-aminocapronic acids, d , l -valine, d , l -leucine, anthranilic acid) with bielectrophilic acylacetylenes proceeds chemo-, regio- and stereospecifically in the presence of NaOH (45–50 °C, 4 h, EtOH–H2O) to give (after treatment of the reaction mixture with aqueous HCl) Z-isomers of N-acylvinyl derivatives of amino acids in 87–94% yield.

The compositions and structures of two new organic metals based on ET [where ET = bis(ethylenedithio)tetrathiafulvalene], viz., (ET)2[Hg(SCN)Cl2], with a metal-dielectric transition temperature (Tm-d) of 35°K, and (ET)2[Hg(SCN)2Br], with Tm-d = 140°K, were established by x-ray diffraction analysis. The crystal structures of the investigated compounds are similar to the structure of the previously studied organic metal (ET)2[Hg(SCN)2Cl] with Tm-d = 50°K. The principal crystallographic data for (ET)2[Hg(SCN)Cl2] are as follows: a = 36.64(1), b = 8.300(4), c = 11.798(1) A, β = 89.91(3)°, V = 3588.1(9) A3, space group Cc, Z = 4, dcalc = 2.05 g/cm3. The principal crystallographic data for (ET)2[Hg(SCN)2Br] are as follows: a = 37.088(14), b = 8.338(3), c = 11.738(5) A, β = 89.71(3)°, V = 3629.6(8) A3, space group C2/c, Z = 8, dcalc = 2.15 g/cm3. A characteristic feature of the crystal structure of the investigated compounds is alternation of the anion and cation layers along the a axis of the crystal. In the cation layer of the k type the ET are interconnected by shortened S...S intermolecular contacts (3.39–3.58 A). The [Hg(SCN)3−nXn]− anions (X = Cl, Br; n = 1, 2) form polymeric chains with one or two bridged SCN groups. A tendency for a decrease in the metal-dielectric transition temperature with a decrease in the volume of the anion is detected in the (ET)2[Hg(SCN)3−nXn] salts, where X = Cl and Br, and n = 1 and 2.

The electrochemical oxidation of ET [bis(ethylenedithio)tetrathiafulvalene] in bromobenzene (electrolyte Bu4N[HgBr3]) gave the radical-cation salt (ET)8[Hg2Br6·PhBr]2 (1), a new organic metal with a temperature range of 300–125 K. At 125 K a metal—dielectric transition is observed. Crystallographic data for (1):a=19.171(6),b=12.668(4),c=17.777(6) A, α=118.03(3), β=89.45(2), γ=101.21(3)°, P\(\overline 1 \),Z=1,dcalc=2.30 g/cm3. The crystal structure of (1) is laminar. In the conducting organic layer the ET radical cations are linked into bands by shortened intermolecular S···S contacts of the “side-to-side” type. The anionic layer consists of centrosymmetric complexes [Hg2Br6·C6H5Br]24−. The Hg1 and Hg2 atoms are characterized by a trigonal configuration of the Hg-Br bond which is built up, on account of secondary Hg···Br interactions, into trigonal-bipyramidal for Hg1 and trigonal-pyramidal (tetrahedral) for Hg2. Interaction between the anionic and cationic layers is effected through Br6...S8 contacts [3.491(7) A)].

The composition and structure of the radical-ion salt (ET)2[Hg(SCN)2Cl], a new organic metal withTM-D=50 K, were established in an x-ray structure investigation. Principal crystallographic data:a=36.69(1),b=8.302(8),c=11.732(8) A, β=90.02(6)°, space groupCc, Z=4,dcalc=2.08 g/cm3,R=0.067. The crystal structure of the salt consists of an alternation of organic (cationic) and inorganic (anionic) layers along the axisa. The anionic layer consists of the polymeric chains in which the [Hg(SCN)2Cl]− ions are linked together along the axisc through secondary Hg···N bonds with lengths of 2.75(3) and 2.98(8) A. On account of these interactions the trigonal configuration of the bonds of the Hg atom is built up to trigonal-bipyramidal. In the organic layer with a structure of the κ type the ET cations form dimers with an interplanar distance of 3.53 A. ET cations belonging to neighboring dimers are linked together through shortened intermolecular S...S contacts with lengths of 3.40–3.50(2) A.

A new three-component reaction between alkyl aryl(hetaryl)ketoximes, acetylene, and aliphatic ketones in the superbasic systems KOH/DMSO and LiOH/CsF/DMSO (70–90 °C, initial acetylene pressure 13–15 atm, 5–60 min) affords novel 4-methylene-3-oxa-1-azabicyclo[3.1.0]hexanes in yields of up to 75%. Using KOH/DMSO, the side products of the reaction are O-vinylketoximes and 2-aryl(hetaryl)pyrroles, while with LiOH/CsF/DMSO, the reaction proves to be selective, only minor amounts of the corresponding alkyl aryl(hetaryl) ketones being detectable.

2-Aminobenzoic acid 1 reacts with α,β-acetylenic γ-hydroxy nitriles 4 and 5 to afford 2-[(5-iminio-2,2-dialkyl-2,5-dihydro-3-furanyl)amino]benzenecarboxylates 7 and 8 (yield 73–74%), a new class of unnatural amino acids in a peculiar zwitterionic form, having the positive charge transferred to the remote imino group of the dihydrofuranyl substituent. 3- and 4-Aminobenzoic acids 2 and 3 with α,β-acetylenic γ-hydroxy nitriles 4–6 undergo entirely different transformations to deliver the esters of cyanomethylhydroxyalkyl ketones 9–12, which result from the unusually facile esterification of the hydroxyl function and simultaneous hydration of the triple bond. 4-Aminobenzoic acid 3 is found to be an active organic catalyst for the one-pot conversion of α,β-acetylenic γ-hydroxy nitrile 4 to 5-amino-2,2-dimethyl-3(2H)-furanone 13, in 80% yield.

3-Phenylamino-5-phenylimino-1,2,4-dithiazole reacted with 1-acyl-2-phenylacetylenes in ethanol or toluene on heating (78–80°C, 1 h) in chemo- and regioselective fashion to give previously unknown N-[5-acyl-3,4-diphenyl-1,3-thiazol-2(3H)-ylidene]-N′-phenylthioureas (yield 57–60%). The structure of N-[5-benzoyl-3,4-diphenyl-1,3-thiazol-2(3H)-ylidene]-N′-phenylthiourea was proved by X-ray analysis.

The new cation-radical salt (EPT)HgCl3 is prepared. Its structure and electrical conductivity are studied. The crystal structure of (EPT)HgCl3 contains (EPT)+ in the chair conformation and trigonal planar HgCl3− packed into organic and inorganic layers alternating along thea axis. Shortened intermolecular contacts join HgCl3− into infinite chains along the c axis (Hg...Cl, 3.289 and 3.387 A), form stacks (S...S, 3.536 and 3.597 A) and layers (S...S, 3.427–3.498 A) of EPT+ cation-radicals, and create cation-anion interactions between neighboring layers in the crystal (Cl...S, 3.396–3.521 A, Cl...C, 3.360 A). The configuration of the bonds around Hg in HgCl3− is distorted trigonal planar: Hg-Cl, 2.342(3)–2.449(3) A, Cl-Hg-Cl, 110.7(1)–137.4(1)∘. The Hg atom lies out of the plane of the Cl atoms by 0.015 A. The conductivity of (EPT)HgCl3 at ∼20°C is σ300 ∼ 5·10−2 (Ω·cm)−1. The dependence of conductivity on temperature is semiconducting in nature.

X-ray structural analysis has revealed that reaction of (BEDT-TTF)[HgCl3]− with PhCl leads to the formation of a cation-radical salt (BEDT-TTF)4[Hg2Cl6]· PhCl, which exhibits a laminar crystal structure. The cationic layer is characterized by a grid or lattice network of contracted S...S intermolecular distances (3.396(4)–3.647(5) A), which unite the BEDT-TTF cations in ribbons or bands, parallel to the [014] direction, and which also bind the ribbons together in a direction close to the [010] axis. The presence of this type of lattice network explains the metallic nature of the conductivity of this salt (BEDT-TTF)4Hg2Cl6]·PhCl in the temperature range 300.0–1.5 K, and is the basis of assigning this salt to a new class of organic, two-dimensional conductors. The [Hg2Cl6]2− anions and PhCl solvent molecules are united via secondary Hg...Cl 3.176(5) A and Cl...Cl 3.480(6) A interaction forces to form centrosymmetric tetramers [Hg2Cl6PhCl]24−, stretched out along the [014] axis direction.

A new organic twodimensional metal (ET) 4 (Hg 2 Cl 6 ·C 6 H 5 Cl) retaining its metallic state down to 1.5 K has been synthesized. It is characterized with the layer-like structure composed of layers of four crystallographically independent cation-radicals of ET and anion layers formed of (Hg 2 Cl 6 ·C 6 H 5 Cl) dimers, solvent molecules being present in their composition. The dimers are interconnected into a centosymmetric fragment (Hg 2 Cl 6 ·C 6 H 5 Cl) 2 .

New ion-radical salts with iodine-cadmiate anions, (BEDT-TTF) 4 -Cd 2 I 6 and (BEDT-TTF) 2 Cd 3 I 6 , have been synthesized and their compositions and structures have been determined with the X-ray analysis. Both compounds are characterized with the alternation of organic layers formed of the BEDT-TTF molecules with inorganic ones composed of discrete anions [Cd 2 I 6 ] 2− in ET 4 Cd 2 I 6 and representing a polymeric net (Cd 3 I 6 ) n in ET 2 Cd 3 I 6 .

9. 10. J. Emsley, D. J. Janes, and R. J. Kurada, Inorg. Nucl. Chem., 43, No. 10, 2243-2246 (1981). C. J. Gilmare and J. C. Speakman, Acta CrystaUogr., B38, 2809-2813 (1982). M. Currie and J. C. Speakman, J. Chem Soc. (A), 1862-1869 (1967). V. K. Trunov and L. N. Kinzhibalo, Dokl. Akad. Nauk SSSR, 263, No. 2, 348-351 (1982). V. A. Efremov, V. K. Trunov, and T. A. Berezina, Kristallografiya, 27, No. 1, 134-139 (1982). V. K. Trunov, V. A. Efremov, and Yu. A. Velikodnyi, Crystal Chemistry and Characteristics of Double Molybdates and Tungstates [in Russian], Nauka, Leningrad (1986). V. A. Efremov, V. K. Trunov, I. Matsichek, et al., Zh. Neorgan. Khim., 26, No. 12, 3215 (1981). W. H. Zachariasen, Acta Crystallogr., 16, No. 11, 1139 (1963). N. Walker and D. Stuart, Acta Crystallogr., A39, 159 (1983).

New molecular conductors on the base of 8,8’-dibromo cobalt bis(dicarbollide) anion, (BEDT-TTF)2[8,8’-Br2-3,3’-Co(1,2-C2B9H10)2] (1), and (BEDT-TTF)[8,8’-Br2-3,3’-Co(1,2-C2B9H10)2] (2) were synthesized and their crystal structures and electrical conductivities were determined. Both radical cation salts prepared were found to be semiconductors. The introduction of two bromine atoms in the cobalt bis(dicarbollide) anion produces a strong effect on crystal structure and electrical conductivity of the prepared materials.

The reaction of α,β-acetylenic γ-hydroxy nitriles with thiosemicarbazide, under mild conditions (rt, no catalyst, in 1:1 aqueous ethanol, 4–14 h), proceeds chemo-, regio- and stereoselectively to give atypically so far inaccessible tri-functionalized (amino, hydroxyl and thioamide groups) pyrazoles in 53–91% yields. The hydroxyl function is easily protected by using the corresponding acetals of the starting acetylenic hydroxy nitriles.

Fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones react with methylamine in different ways, depending on the substrate structure. Arylhydrazones having a short fluoroalkyl substituent (RF = CF3, HCF2CF2) react at the carbonyl group adjacent to the nonfluorinated substituent to give 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones. Arylhydrazones with a long-chain fluoroalkyl group (RF = C3F7 and longer) and a bulky nonfluorinated group take up methylamine molecule at the carbonyl group linked to the fluorinated substituent, and the subsequent haloform reaction yields N-methyl-2-arylhydrazono-3-oxobutanamides. Both types of products are formed in reactions of methylamine with 1,2,3-triketone 2-arylhydrazones having a long fluoroalkyl group and methyl group at the other carbonyl group. Template condensation of fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones with methylamine over Ni(II) template gives bis[3-alkyl(aryl)-1-polyfluoroalkyl-3-methylamino-2-aryldiazenylprop-2-en-1-onato-N,N′]-nickel(II), regardless of the size of the fluoroalkyl substituent. The same complexes and their copper analogs can be obtained by treatment of 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones with the corresponding metal salts.

Condensation of ethyl 3-polyfluoroalkyl-3-oxopropionates with excess triethyl orthoformate gave ethyl 3-polyfluoroalkyl-2-ethoxymethylidene-3-oxopropionates which reacted with primary aliphatic, aromatic, and heterocyclic amines to form ethyl 2-alkyl(aryl, hetaryl)aminomethylidene-3-polyfluoroalkyl-3-oxopropionates. According to the X-ray diffraction and IR data, the latter exist in the crystalline state as the corresponding E isomers, while in solution (NMR data), as mixtures of Z and E isomers. Condensation of ethyl 2-ethoxymethylidene-3-oxopropionates with secondary heterocyclic amines (morpholine and pyrrolidine) led to the formation of 2-morpholino(pyrrolidin-1-yl)methylidene-3-fluoroalkyl-3-oxopropionates which were shown to exist as Z isomers both in the crystalline state and in solution.

The structure of a new organic conductor, (BEDT-TTF) 4 Hg 3 I 8 , has been solved, temperature dependences on conductivity, thermopower and magnetic susceptibility studied. The BEDT-TTF molecules form two different types of stacks. At 260 K a jump in a conductor and thermopower takes place, characterized by a hysteresis of ca. 8 K. At this temperature the phase transition of the first order occurs in (BEDT-TTF) 4 Hg 3 I 8 . Below and above the transition temperature the conductivity has an activation character. At a pressure of 29 kbar the conductivity remains metallic up to 50 K. The paramagnetic susceptibility in this temperature range has a maximum

1H and13C NMR, x-ray structural analysis, and magnetic moment measurements have shown that in 5-thio(seleno)pyrazolealdiminate complexes of nickel(II) based on tetradentate ligands containing the fragment , with n=2, flattening of the chelate unit takes place in solution and in the solid state. A similar structure in which the diamine metal-containing ring has the twist-chair conformation is observed for the crystals of the complexes with n=4. For the complexes with n=4 in solution at a temperature below −50°C, rapid (on the NMR time scale) interconversion of the flattened (P) (S=0) and pseudotetrahedral (T) (S=1) structures is observed, not accompanied by inversion of the tetrahedral configuration of the metal atom. At temperatures above −50°C, in addition to the low-barrier reactions (T) ⇄ (P), conversion of the seven-membered saturated metal-containing ring and inversion of the tetrahedral configuration of the Ni atom with activation barriers of 48–51 kJ/mole are observed.

The structure of 5-methyl-3-(1-methyl-3-isopropoxyallyl)-1-formyl-3,4,4-tricyano-1-cyclopentene was determined by an x-ray diffraction structural analysis. A discussion was given for the pseudoaxial orientation of the C≡N and C-H groups at the 3,5-positions, steric strain, the effect of this strain leading to a large ring flexure angle and extension of the C-C bonds, the bipolar nature of the enaminoformyl fragment, twisting of the NH2 group due to an unusual intramolecular hydrogen bond involving the ethereal oxygen atom, the lack of extension of the $$\begin{array}{*{20}c} \setminus \\ / \\ \end{array} C = C\begin{array}{*{20}c} / \\ \setminus \\ \end{array} $$ bond under conditions of np(O)−π*(C=C) conjugation, and the conformation of the isopropyl group relative to the O-C(sp3) bond.

A new C70-based molecular complex 4BNDY·3C70·4C6H6 (1) (BNDY is binaphtho[1,8-d.e]-1,3-dithiin-2-ylidene) was prepared, and its full X-ray diffraction study at room temperature was performed. The C70 molecules in crystal 1 are ordered in different ways, and their ordering depends on van der Waals interactions between them and nonplanar BNDY molecules in the boat conformation. The neighboring BNDY molecules in the structure are bound to each other by π-π interactions.

A new procedure was developed for the synthesis of 6-phenyltetrazolo[1,5-b]triazin-7-one. Aza analogs of uracil and isocytosine were prepared by the tetrazole ring cleavage. It was demonstrated that these transformations can be used in the synthesis of anomalous nucleosides.

An X-ray structural investigation of a new molecular semiconductor. [Pd(dddt) 2 ] 2 CF 3 SO 3 (1), where dddt 2- is 5,6-dihydro-1,4-dithiin-2,3-dithiolate, is made. Crystal data of 1: a = 6.521(7) A, b = 8.354(4) A, c = 16.113(6 ) A, α = 87.12(4)°, β = 85.51(6)°, γ = 67.94(7)°, V = 811(1) A 3 , triclinic, space group P1. Crystal structure 1 is characterized by layers of [Pd(dddt) 2 ] 1/2+ radical cations, with [CF 3 SO 3 ] - anions located between them. In these layers, [Pd(dddt) 2 ] 1/2+ cations form dimers with strongly shortened intermolecular contacts Pd...Pd 3.031(2) A. The [CF 3 SO 3 ] - anion in the structure of 1 is disordered.

Conformational study of 2-phenylazo-1-vinylpyrrole and 2-(4-bromophenyl)azo-5-methyl-1-vinylpyrrole was performed on the basis of the experimental measurements and high-level ab initio calculations of their 13C--13C and 13C--1H spin-spin coupling constants, showing marked stereochemical behaviour upon the internal rotation of the vinyl group and the pyrrolyl moiety. In liquid phase, both compounds were found to adopt predominant s-trans-s-trans conformation with the noticeable population (ca. 30%) of the higher-energy s-cis-s-trans conformation in the latter compound. As follows from the X-ray data, 2-phenylazo-1-vinylpyrrole crystallizes in s-trans-s-trans conformation while the crystalline molecular structure of 2-(4-bromophenyl)azo-5-methyl-1-vinylpyrrole is s-cis-s-trans.

Polyhaloalkyl-substituted chromones, gamma-pyrones, and beta-furanones react with salicylaldehydes in the presence of piperidine to give a wide variety of fused 2H-chromenes in good yields. This novel annulation reaction presumably proceeds by a tandem intermolecular oxa-Michael addition and subsequent intramolecular Mannich condensation.

Tri-and tetracyclic compounds were synthesized by the cyclization of 6-alkoxy-2,3-dicyano-5-nitromethyl-1,4,5,6-tetrahydropyrazines with 1,2,3-triazinium and quinoxalinium cations.

A simple procedure for the synthesis of N,N,N′-trialkyl-1,8-diaminonaphthalenes is described. It consists in partial demethylation (dealkylation) of commercially available proton sponge [1,8-bis(dimethylamino)naphthalene] and some of its derivatives at heating with HBr–KI–DMF system. Limitation, scope and a possible mechanistic pathway for the reaction are discussed. For isomeric 8-dimethylamino-1-methylamino- and 1-dimethylamino-8-methylamino-4-nitronaphthalenes, X-ray measurements have been conducted. The first examples of complete realkylation reactions in the naphthalene proton sponges are reported.

Two new radical cation salts based on bis(ethylenedioxy)tetrathiafulvalene (BEDO) with the square planar Ni(CN)42− anion, (BEDO)4Ni(CN)4·4CH3CN (1) and (BEDO)5Ni(CN)4·3C2H4(OH)2 (2), were synthesized by electrocrystallization. The X-ray structural analysis, electrical transport and magnetotransport properties as well as the calculated Fermi surfaces are presented and discussed. Both salts show metallic properties down to 4.2 K. The nature of the Fermi surface of both salts is discussed and compared with those of other β″ type BEDO salts. On the basis of this comparison it is suggested that salt 2 is a likely candidate to exhibit magnetic breakdown and quantum interference effects in the magnetoresistance. It is shown that salt 1 exhibits unconventional magnetotransport behavior.

A new charge transfer salt of (BEDO-TTF) 4 Pt(CN) 4 ·H 2 O (BEDO-TTF = bis(ethylenedioxo)tetrathiafulvalene) composition has been prepared. X-ray analysis shows that the conducting donor layers of new θ″-type packing alternate with anion sheets composed of [Pt(CN) 4 ] −2 anions, which are associated with H 2 O molecules via hydrogen bonds. Temperature and magnetic field dependences of the resistance are presented.

A series of electroconducting cationic salts based on the Pd(dddt) 2 and Ni(dddt) 2 complexes has been synthesized. The first stable molecular metals have been found among the M(dddt) 2 salt family.

Extraction of fullerenes from carbon soot by trichloroethylene has been studied. We have found that C60 forms a solvate with trichloroethylene (C60 · C2HCl3:a=31.31(1);b= 10.156(4);c=10.146(4) A;V=3228.6 A3,Z=4,dcalc=1.752 g cm−3, orthorhombic symmetry). Its thermal stability has been studied using TG and DSC. A phase transition of the first order at 167 K has been detected.

The crystal data for bis(4,4,5,5-trisulfano-1,3-dithiole-2-thione) are: C 6 S 12 , M = 456.8, orthorhombic, P 2 1 2 1 2 1 , a = 7.940(2), b = 9.654(2), c = 19.428(4) A , V = 1489.2(6) A 3 , Z = 4, D x = 2.037 Mg/M 3 , λ( Mo K α) = 0.710 69 A , μ = 1.669 mm −1 , F (000) = 912, T = 290 K, R = 0.028, Rω = 0.021 for 923 observed reflections with I > 2 σ ( I ). In the C 6 S 12 molecule, two C 6 S 5 groups (dmit groups) are attached to one another via trisulfane bridges and so form the ten-membered cycle, consisting of four carbon and six sulfur atoms, with respect to which both the dmit groups are in cis -configuration. The symmetry of the C 6 S 12 molecule is close to mm 2.

A neutral metal complex, [Pt(dddt)2]° (1), has been obtained by oxidation of the [Pt(dddt)2]− anion with excess (Bu4N)AuBr4 in nitrobenzene. Crystallographic data for 1∶a=17.854(9) A,b=18.409(9) A,c=4.717(5) A, γ=68.83(2)°, space group P21/n,Z=4,d calc=2.55 g/cm3. In1 two independent centrosymmetric [Pt(dddt)2]° molecules are packed in stacks that form layers parallel to the (110) plane. The molecules of1 in the layers have shortened S...S contacts 3.491(9) A, and 3.594(10) A. The average bond lengths Pt-S 2.242(7) A, S-C 1.71(2) A and C=C 1.40(3) A, together with the square-planar coordination of Pt in PtS4, suggest considerable conjugation in the metal cycles.

The radical cation salt ET(NCS)0.77 [bis(ethylenedithio)tetrathiafulvalene thiocyanate (1/0.77)] has been prepared for the first time by electrocrystallization and its crystal and electronic structure at 110 K was investigated. The unit-cell dimensions are orthorhombic, a = 6.638 (1), b = 8.309 (2), c = 28.776 (6) Å, V = 1587.1 (6) Å3, space group Pbcm, Z = 4. The compound has a layered structure. The ET radical cations of the conducting cationic layer build stacks. In the anionic layer the thiocyanate groups form polymeric chains where they are oriented in a `head-to-tail' mode. The structure has short intermolecular contacts of the cation–cation, anion–anion and cation–anion types, which leads to the formation of a three-dimensional structure of intermolecular interactions. This phenomenon is very rare in molecular conductors. Tight binding band structure calculations suggest, however, that the interlayer interactions through the anions are weak and that the incomplete occupation of the anion sites is the reason for the activated conductivity of the salt.

X-ray diffraction structural analysis, IR,13C NMR, and PMR spectroscopy was used to establish that the products of the reactions of arylhydrazonoyl chlorides of ethyl oxalate and sodium ethylate are 1,4-diaryl-3,6-dicarboethoxy-1,4-dihydro-1,2,4,5-tetrazines and 1-aryl-3-carboethoxy-4-arylhydrazono-5-pyrazolones.

The new molecular semiconductor (ET)5[Ho(NCS)7]·EtOH was synthesised by the electrochemical oxidation of bis(ethylenedithio) tetrathiafulvalene (ET); its crystal structure and electroconducting properties were studied.

A series of novel non-symmetrical coumarin-fused BODIPY dyes were synthesised. Their absorption and emission properties are strongly influenced by substitution in the coumarin moiety. Diethylamino-substituted dyes showed near-IR emission with large Stokes shifts (up to 144 nm) and good fluorescence quantum yields.

A new room temperature metallic modification of the well known α-(ET)2[KHg(SCN)4] salt has been prepared by electrochemical oxidation of ET. Its crystal and electronic structure as well as the conducting properties have been examined. The salt has a layered structure like the δ-(ET)2[KHg(SCN)4] phase.

Summary form only given. The galvanostatic electrochemical oxidation of BEDO-TTF has been carried out in the presence of Nbu/sub 4/HgX/sub 3//HgX/sub 2/Nbu/sub 4/X (X=Br, I) system as a supporting electrolyte. Varying the relation of the components, we have isolated at least two phases of BEDO-TTF mercury bromides and two phases of BEDO-TTF mercury iodides. X-Ray analysis of the crystal structure is now being carried out. The compounds exhibit metallic conductivities down to helium temperatures, like those described in [1]. Phase transition in the range of about 70 K has been - shown for BEDO-TTF mercury iodides. Pressure dependences of resistivity have been investigated. 1. H. Tajima et al Solid State Commun. 86, 7(1993).

Summary form only given. The oxidation of ET in the presence of CuSCN + Hg(SCN) + RSCN + crown ether electrolyte is investigated for the preparation of ET salts, in which an inorganic layer contains Cu(I) and Hg(II). It is established, that varying Hg:Cu:SCN ratio one can obtain 1) crystals of the superconductor (ET)/sub 2/CU(NCS)/sub 2/ with a sharp superconducting transition at T/sub c/ =10.4 K 2) crystals with a metallic conductivity down to 20 K 3) crystals of ET/sub 5/[CuHg(SCN)/sub 4/]/sub 2/ with a semiconducting behavior. The composition and the structure of the latter is determined by using X-ray analysis. It was found that ET layers contain the stacks composed of 5 independent cation-radicals. These layers alter with the anion layers, which contain polymerized -(Cu-NCS-Hg)- chains with an elementary (Hg(SCN)/sub 4/Cu)/sub n/- unit. All Hg and Cu atoms form covalent bonds with SCN ligand.

Summary form only given. An x-ray study of a crystal of new organic metal (ET)/sub 4/Hg/sub 3/Br/sub 8/ with T/sub M-D/ =20 K has been made. The crystal structure is similar to the crystals of organic superconductors (ET)/sub 4/Hg/sub 2.89/Br/sub 8/ (T/sub c/ =4.3 K) (2) and (ET)/sub 2/Hg/sub 1.41/Br/sub 8/ (T/sub c/ =2.0 K) (3). An x-ray study of crystals 1-3 allows us to assume that the anion layers consist of HgBr/sub 4//sup 2-/ ions and HgBr/sub 2/, neutral molecule alterating in the crystal in an arbitrary way. In the conducting layers of crystals 1-3, the ET are packed according to the k-type. Each cation-radical has 12 shortened S...S contacts. The atomic-atomic potentials calculations show that, the energies of intermolecular interactions in the conducting layers of crystals 1-3 are the same, 33.6 kcal/mol. At the same time, the interplanar distance between the neighbours in the ET dimer are different, being equal to 3.51(l), 3.44(l) and 3.42(3) /spl Aring/ in structural 1-3 respectively. The structure 1 is also different from 2 and 3 in stronger cation-anion interactions: the Br ... S distances are 3.59(l), 3.64(l) and 3.64(l) /spl Aring/ respectively. We believe that the discovered differences in the structure of crystals 1-3 may account for the differences in the electronductive properties.

Summary form only given. Structural resistivity and EPR study of the single crystal (Hg-ET)/sub 2/Hg(SCN)/sub 2/Br and its deuterated analog (D/sub 8-ET)/sub 2/Hg(SNC)/sub 2/ Br are presented. These salts belong to the -type structure class of organic conductors. Temperature dependence of ESR linewidth for these salts are very similar to that of conductivity. The first-order phase transition with localization of the electrons on ET dimers at 100K are found for hydrogen-containing salt, wheras two phase transition of semiconductor-semiconductor tye and possible magnetic ordering at low temperatures (near 10K) are found for deuterium containing compound. The drastic isotope effect in these compound is considered to be associate with hydrogen bond between terminal CH-groups of cationic sheet and Br-atom in anionic sheet in hydrogen containing compound.

The new complex of [60]fullerene with bis(methylenedithiotetrathiafulvalene) (MT) was studied by an X-ray analysis. The main crystal data for C 60 ·(MT)·2(CS 2 ) ( 1 ): M =1229.45, monoclinic, a =13.550(5) A, b =9.964(7) A, c =17.125(8) A, α =99.52(4)°, V =2280(2) A 3 , space group P2 1 /m. The crystal structure of 1 is built up of C 60 layers which alternate with the layers consisting of MT and CS 2 molecules. There are shortened contacts between C 60 and donor molecule that gives rise to a change of the MT geometry. The donor molecules in 1 are connected by the shortened S⋯S intermolecular contacts that discovered for the first time for the CTC based on [60]fullerene.