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We report the preparation, crystallization, and solid-state characterization of a benzyl-substituted spirobiphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state, with the molecules packed in an unusual one-dimensional (1-D) fashion that we refer to as a pi-step stack. This particular mode of 1-D stacking is forced on the lattice arrangement by the presence of the orthogonal phenalenyl units that were specifically incorporated to prevent the crystallization of low-dimensional structures. The structure shows that this strategy is effective, and neighboring molecules in the stack can only interact via the overlap of one pair of active (spin-bearing) carbon atoms per phenalenyl unit, leading to the pi-step structure in which the remaining four active carbon atoms per phenalenyl unit do not interact with nearest neighbor molecules. The magnetic susceptibility data in the temperature range 4-360 K may be fit to an antiferromagnetic Heisenberg S = 1/2 linear chain model with intrachain spin coupling J = -52.3 cm(-1). Despite the uniform stacking, the material has a room temperature conductivity of 1.4 x 10(-3) S/cm and is best described as a Mott insulator.

A simple and general route to the synthesis of organocobaloxime with mixed dioxime ligands, RCo(L)(dpgH)Py [L = dmgH and chgH] (R = Me-Dec), has been described. The crystal structure of four complexes, ClCo(L)(dpgH)Py and MeCo(L)(dpgH)Py [L = dmgH and chgH], is reported. The structural study reveals that both the nonclassical C−H···O as well as the classical O−H···O intermolecular hydrogen bonding is present and leads to the formation of one-dimensional dimeric or polymeric structures. 1H and 13C NMR coordination shifts in the axial pyridine ligand show clear correlations with the chemical shift of the equatorial ligand. These correlations can be rationalized with the aid of the ring current model.

We report the crystal structure of a spiro-bis(1,9-disubstituted-phenalenyl)boron cation ( 2 + ) and by comparison with the structures of a series of radicals we conclude that the changes in bond lengths in the radicals compared to those of the corresponding cation can be qualitatively predicted by the sign of the partial bond order of the singly occupied molecular orbital (SOMO), which contains the additional electron. By use of this information, we can analyse the structures of the π-dimer radicals 1 and 2 and ascertain the location of the unpaired electron in these compounds. Where these radicals exist as paramagnetic π-dimers (high-temperature regime), the unpaired electrons reside mainly in the phenalenyl units not directly involved in the π-dimer interaction. At low temperatures, where the diamagnetic π-dimers exist, the electrons localise in the phenalenyl units directly involved in the π-dimer, but there still exists some degree of delocalisation of the electrons to the other halves of the molecules. We postulate that the increase in delocalisation of the unpaired electrons is related to the increase of the conductivity by about two orders of magnitude as the electrons spin pair.

A new class of phenalenyl-based neutral radical molecular conductors has recently been reported; a distinctive feature of these molecular solids is the absence of the well-defined conducting pathway(s) that are characteristic of the organic charge- transfer salts. These radicals do not stack in the solid state, and the requisite carbon- carbon contacts are all larger than the sum of the van der Waals distances. Magnetic susceptibility measurements show that these compounds usually exist as isolated free radicals with one spin per molecule (at least over some temperature range), apparently supporting the idea that there is little interaction between the molecules in the solid state. Nevertheless, these radicals show the highest conductivity (RT 0.05 S/cm) of any neutral organic solid and the conduction mechanism is at present unresolved. In this article we report a structurally related radical with a resistivity five orders of magnitude higher than that of the previously reported radicals. We analyze the crystallographic and electronic structure of this solid in detail and point out some of the challenges that remain in relating structure, magnetism, and conductivity in this new class of organic solids. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 95: 853- 865, 2003

The passage of a current through a solid requires a pathway for the movement of electrons or holes. A new class of phenalenyl-based neutral radical molecular conductors has recently been reported; a distinctive feature of these molecular solids is the absence of any obvious conducting pathway(s). These radicals do not stack in the solid state, and the requisite carbon−carbon contacts are all larger than the sum of the van der Waals distances. Magnetic susceptibility measurements show that the first compound to be isolated behaves as a free radical with one spin per molecule, apparently supporting the idea that there is little interaction between the molecules in the solid state. Nevertheless, this radical shows the highest conductivity (σRT = 0.05 S/cm), of any neutral organic solid, and the conduction mechanism is presently unresolved. In the present study, we report a structurally related radical with a resistivity 4 orders of magnitude higher than that of the previously reported radicals. We analyze th...

The preparation and crystal structure of 5-cyanofuran-2-[1,2,3,5-diselenadiazolyl], [RCN(2)Se(2)] (R = 5-cyanofuran), is reported. Crystal data for C(6)H(2)ON(3)Se(2): monoclinic, space group P2(1), a = 7.1121(7), b= 20.541(2), c =20.923(2) A, beta = 99.785(1) degrees, Z = 16. The crystal structure consists of diselenadiazolyl pi-dimer stacks running parallel to the x direction; the asymmetric unit consists of four pi-dimer units. The dimers are aligned into snakelike ribbons along the y direction, with consecutive dimers linked by head-to-tail CN-Se contacts. Each pi-dimer stack is bordered by two out-of-register stacks, but most interstack Se-Se contacts lie outside the van der Waals separation. Along the pi-dimer stacks, the intradimer Se-Se distances range from 3.183(10) to 3.294(1) A, and the interdimer Se-Se distances range from 3.826(1) to 3.945(1) A. Like other pi-dimer stacked diselenadiazolyls, [C(6)H(2)ON(3)Se(2)](2) is diamagnetic over the temperature range 4-380K. Variable temperature single-crystal conductivity measurements reveal a room-temperature conductivity near 10(-5) S cm(-1) and provide a calculated band gap of 0.72 eV. The structural results and transport properties are interpreted in the light of Extended Hückel band structure calculations.

The present paper deals with the microstructural parameters calculated from X-ray diffraction data, electrical and optical investigations, and scanning tunneling microscopy (STM) studies on ZnIn2S4 IIIa layer type CdIn2S4-xSex (1.75 ≤ x ≤ 2.75) quaternary chalcogenides. Microstructural parameters such as dislocation density, root-mean-square strain, stacking fault probability, crystallite size anisotropy, and layer disorder parameters of these compounds have been calculated. The temperature variation of electrical conductivity (25−400 °C) confirmed semiconducting behavior. The band gaps of all these compounds obtained from STM and optical measurements are in the range 1.57−1.77 eV and are comparable to each other irrespective of the technique used.

Reactions of bis[diphenyl-3-(4-methoxyphenylsydnonyl)]phosphine palladium chloride and amines yielded trans-amminedichloropalladium complexes, which were characterized by spectroscopic techniques (compounds 5–9) and X-ray diffraction (compounds 5 and 7). Bond lengths of PC(10), P-(16) decrease more than that of P-(1) after the complex is formed, suggesting that the phenyl rings are able to contribute more electron density to phosphorus for binding with Pd(II) than the sydnone ring. The equilibrium constants and rate constants for the reaction between complex 4 and amines depend not only on the basicity but also on the steric size of amines used.

A simple and general route to the synthesis of cobaloxime with mixed dioxime ligands, XCo(L)(L′)Py, L,L′=dmgH/dpgH and chgH/dpgH; X=Cl, Br, NO2, N3, has been described. These compounds are reported for the first time. The synthesis is confirmed by the X-ray structures of N3Co(dmgH)(dpgH)Py and N3Co(chgH)(dpgH)Py. The cis and trans effects on these complexes and on XCo(L)2Py (L=dmgH, chgH, dpgH; X=Cl, Br, NO2, N3) complexes have been studied by 1H-, 13C-NMR, UV, and X-ray. For a range of X ligands, a clear trend between the 1H, 13C chemical shifts of the equatorial and axial ligands as well as with the Co–dioxime CT band has been observed. The analysis of the 13C values and X-ray data shows that one dioxime wing effects the other dioxime wing in the mixed dioxime complexes.

A simple and general route to the synthesis of organocobaloxime with mixed dioxime ligands, RCo(dmgH)(dpgH)Py and RCo(chgH)(dpgH)Py, has been described. The 13C-NMR chemical shifts have been analysed to see whether one dioxime wing has any effect on the other dioxime wing. The first crystal structure of an organocobaloxime with mixed dioxime ligand in the same complex, BnCo(dmgH)(dpgH)Py and BnCo(chgH)(dpgH)Py, is reported.

Dissolution of [CpRu(PPh 3 )(SC 4 H 8 ) 2 ]CF 3 SO 3 in thietane/CH 2 Cl 2 with stirring yields the title compound [CpRu(PPh 3 )(SC 3 H 6 ) 2 ]CF 3 SO 3 ( I ). The single crystal X-ray structure shows a disparity in the puckering of the two thietanes. One thietane ligand is near-planar, with torsion angles of ±1.5(5)° for CSCC and ±1.8(4)° for CCCS; the second thietane ligand of I has torsion angles of ±21.0(4)° for CSCC and ±25.0(3)° for CCCS. Compound I contains both the largest and the smallest torsion angles for any complex reported. Theoretical calculations were carried out for both thietane and for I using the gamess and gaussian 98 packages.

Bifunctional 1,2,3-dithiazoles bridged with azine and phenylenediamine spacers have been prepared, with a view to determining the extent of communication between the two dithiazole rings as a function of the electronic and steric demands of the bridge. The crystal structure of the closed-shell diazine derivative [S(2)NClC(2)=NN=C(2)ClNS(2)] is rigorously planar. Cyclic voltammetry on this compound indicates two reversible one-electron oxidations. The radical cation state has been characterized by EPR spectroscopy and by crystal structure determination of its 1:1 PF(6)(-) salt. The latter reveals little interaction between neighboring radical cations; consistently, the material exhibits a conductivity of sigma10(-5) S cm(-1). Insertion of a phenylene group into the diazine bridge to afford [S(2)NClC(2)=NC(6)H(4)N=C(2)ClNS(2)] leads to significant torsional motion between the phenylene ring and the two end groups, as a result of which the two DTA rings are electronically independent; no radical cation state has been observed for this species. Crystal data for Cl(2)S(4)N(4)C(4): a = 5.1469(15), b = 13.343(2), c = 14.2031(17), orthorhombic, Pbca, Z = 4. Crystal data for Cl(2)S(4)N(4)C(4)PF(6): a = 11.699(4), b = 12.753(5), c = 10.461(4), beta = 112.17(1) degrees, monoclinic, C2/c, Z = 4. Crystal data for C(l2)S(4)N(4)C(10)H(4): a = 3.9477(6), b = 23.790(3), c = 7.3769(9), beta =90.793(12) degrees, monoclinic, P2(1)/c, Z = 2.

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- and butyl (4)-substituted spiro-biphenalenyl radicals. Both of these compounds are found to be conducting face-to-face pi-dimers in the solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic pi-dimer (interplanar separation of approximately 3.1 A), whereas 3 is a paramagnetic pi-dimer (interplanar separation of approximately 3.3 A), and both compounds show phase transitions between the paramagnetic and diamagnetic forms. Electrical resistivity measurements of single crystals of 3 and 4 show that the transition from the high-temperature paramagnetic pi-dimer form to the low-temperature diamagnetic pi-dimer structure is accompanied by an increase in conductivity by about 2 orders of magnitude. This behavior is unprecedented and is very difficult to reconcile with the usual understanding of a Peierls dimerization, which inevitably leads to an insulating ground state. We tentatively assign the enhancement in the conductivity to a decrease in the on-site Coulombic correlation energy (U), as the dimers form a super-molecule with twice the amount of conjugation.

A synthetic scheme leading to the (X)(Y)bis(1,2-cyclohexanedionedioximato)cobalt(III) complexes, where X=Cl, N 3 , ClCH 2 , CH 3 , C 2 H 5 and Y=PPh 3 and Py is reported. The complexes have been characterized by the usual spectroscopic techniques and have been compared with the reported analogous compounds having other dioximes as the equatorial ligands. The first crystal structure of an inorganic cobaloxime with 1,2-cyclohexanedionedioxime (Nioxime) is reported. For a range of X ligands, a clear trend between 31 P, 13 C, 1 H chemical shifts of the equatorial and axial ligands as well as with the Co→chgH charge transfer band has been observed.

Monomeric five-coordinate nickel−cysteine complexes were prepared using anionic tris(3,5-disubstituted pyrazolyl)borates (Tp* - and TpPhMe-) and l-cysteine (ethyl ester and amino acid forms). Tp*NiCysEt crystallizes with a single methanol of solvation in the monoclinic space group P21: a = 7.8145(18), b = 24.201(6), c = 7.9925(14) A; β = 117.991(16)°. [Tp*NiCys-][K+] and TpPhMeNiCysEt show magnetic and electronic characteristics similar to Tp*NiCysEt, so that the trigonal bipyramidal coordination geometry confirmed for Tp*NiCysEt in the solid state likely applies to all three. All three complexes have high spin magnetic ground states at room temperature (μeff = 2.9−3.2 μB, S =1). Their electronic spectra are dominated by sulfur to nickel charge-transfer bands (388−430 nm in chloroform) with energies that correlate to respective thiolate basicities and TpX- donor strengths. The Tp* derivatives undergo a rapid reaction with molecular oxygen. Stoichiometric, infrared, and electronic spectroscopy measurement...

We report the preparation, crystallization, and solid-state characterization of a spiro-biphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state and withou...

Reductive coupling of 4,5-dichloro-1,2,3-dithiazolylium chloride yields trans-4,4‘-dichloro-1,1‘,2,2‘,3,3‘-tetrathiadiazafulvalene (DC-TAF), the first example of this heterofulvalene system. Ab initio molecular orbital (B3LYP/6-31G**) calculations on prototypal TAF confirm that the closed shell 1Ag state lies 22 kcal mol-1 below the 3Bu diradical triplet. Cyclic voltammetry on DC-TAF reveals two reversible oxidation waves at 0.80 and 1.25 V (in CH3CN, reference SCE). The ESR signal (g = 2.0117) of the radical cation [DC-TAF]+ (in SO2(l)) exhibits a five-line hyperfine coupling pattern with aN = 0.096 mT. DC-TAF forms a series of 1:1 radical ion salts [DC-TAF][X] by electrooxidation in the presence of tetrahedral counterions (X- = BF4-, ClO4-, FSO3-). The crystal structures of these salts are isomorphous, monoclinic space group P21/n, and consist of one-dimensional ladder-like arrays of [DC-TAF]+ radical cations bridged by S- - -S contacts ranging from 3.5 to 3.7 A. Variable-temperature conductivity and ma...

The synthesis and solid-state characterization of the heterocyclic π-radical 1,2,5-thiadiazolo[3,4-b]-1,2,3-dithiazolo[3,4-b]pyrazin-2-yl, 1,2,3-TDTA, is described. The ESR spectrum of 1,2,3-TDTA (in CH2Cl2, 293 K, g = 2.009) confirms a highly delocalized spin distribution, with observable hyperfine coupling to all five nitrogen atoms of the tricyclic molecule (aN = 0.514, 0.343, 0.109, 0.051, and 0.045 mT). While chemical and electrochemical oxidation (E1/2(ox) = 1.14 V vs SCE) of 1,2,3-TDTA requires relatively harsh conditions, reduction is extremely facile (E1/2(red) = 0.15 V vs SCE). More importantly both the observed cell potential Ecell and computed (MNDO) gas-phase enthalpy ΔHdisp for the disproportionation of this and other 1,2,3-dithiazolyls are significantly lower than those observed for their 1,3,2-isomers. Crystals of 1,2,3-TDTA are monoclinic P21/n, with a = 6.6749(16) A, b = 11.7178(14) A, c = 8.6148(14) A, β = 103.297(16)°, and Z = 4. The crystal structure consists of slipped stacks of head...

The isolation and characterization of [CpRu(9S3)](O3SCF3), where 9S3 = 1,4,7-trithiacyclononane, is reported. The title compound crystallizes in the orthorhombic space group Pbca: a = 10.2542(18), b = 14.8991(13), c = 22.4832(18) A, and Z = 8. The Ru atom is sandwiched between the π-bound cyclopentadienyl ligand and the 9S3 ligand, bonding to all three of the sulfur atoms in the 9S3. The Ru—S distances are 2.2991(10), 2.2979(11), and 2.3055(10) A. The C—S distances range from 1.819(4) to 1.852(5) A in the trithiacyclononane ring.

The reactions of chlorocyclophosphazenes N3P3Cl6 (1) and N4P4Cl8 (2) and polydichlorophosphazene (3) with cyclohexylamine, cyclopentylamine, and cyclopropylamine have been studied. The major product with 1 is the geminal tetrakis derivative N3P3Cl2(NHR)4, while 2 gives the completely substituted derivative, N4P4(NHR)8. X-ray crystal structure determinations of N3P3Cl2(NHC6H11)4 (1a) and N4P4(NHC3H5)8 (2c) have been carried out. 1a crystallizes in a triclinic space group, P1, with a = 11.2330(13) A, b = 11.4269(16) A, c = 13.4055(12) A, α = 72.211(10)°, β = 72.150(9)°, γ = 81.777(11)°, V = 1557.3(3) A3, and Z = 2. 2c crystallizes in a monclinic space group, P21/n, with a = 12.433(3) A, b = 20.484(4) A, c = 12.645(3) A, β = 92.81(2)°, V = 1557.3(3) A3, and Z = 4. The cycloalkylamino-substituted polyphosphazenes contain a small amount of residual chlorine atoms. These have high glass transition temperatures.

The structure of 4,4'-bipyridinium diiodide has been determined. The diprotonated cation possesses crystallographic inversion symmetry with the pyridyl rings coplanar. The crystal packing is dominated by weak but directional N-H···I (N···I distance of 3.47(2) A) and C-H···I (C···I distances of 3.74(3)3.77(3) A) interactions to give layers of ions. The layers stack parallel to the (101) direction and are linked together by an additional C-H···I interaction (C···I distance of 3.816(5) A). Crystal data: triclinic, P-1 (No. 2), a = 8.2940(13), b = 8.3842(11), c = 5.0978(8) A, a = 93.761(11)°, s = 112.281(12)°, ? = 106.887(11)°, V = 307.63(8) A3, Z = 1, Scalc = 2.22 g/cm3. Final residual values based on 997 observed (I > 2s(I)) reflections: R = 0.026, Rw = 0.034.

A comparative study of the structural parameters of bis(dioxime) vitamin B12 models reveal an interesting squeezing of the metallabicycle. The lateral compression and the butterfly bending angle have a common origin in the steric bulk of the dioxime substituents. The first crystal structure of an organocobaloxime with cyclohexanedionedioxime(chgH) as the equatorial ligand is also reported. The compound MeCo(chgH)2Py crystallises in the monoclinic system, with the space group P21/n with Z=4 and unit cell parameters a=8.7074(9), b=9.3989(8), c=23.886(2) A and β=91.862(8)°.

The characterization of the heterocyclic radical 1,2,5-thiadiazolo[3,4-b]-1,3,2-dithiazolo[3,4-b]pyrazin-2-yl (TDP-DTA) is described. The compound is prepared by treatment of 5,6-dithiolo-1,2,5-thiadiazolo[3,4-b]pyrazine with S3N3Cl3 and purified by fractional sublimation in vacuo. The results of cyclic voltammetry and ESR analysis of TDP-DTA and related heterocyclic dithiazolyls indicate that the spin distributions and donor/acceptor properties of these radicals are extremely sensitive to the nature of the 4,5-substituents. The crystal structure of TDP-DTA has been determined at two temperatures. At 293 K, the crystals are triclinic, space group P1, with a = 4.4456(8), b = 8.407(2), c = 9.671(3) A, α = 71.34(2), β = 89.28(2), γ = 87.80(2)°, Z = 2 (for C4N5S3); at 150 K the crystals are triclinic, space group P1, with a = 7.489(7), b = 9.593(4), c = 10.759(6) A, α = 65.77(4), β = 74.10(6), γ = 74.64(6)°, Z = 2 (for C8N10S6). At 293 K the structure consists of ribbons of TDP-DTA radicals packed in a slip...

The condensation of diaminobenzenedithiol with sulfur monochloride leads to the chloride salt of the radical cation of 3,6-dichlorobenzo(1,2-d:4,5-d')bis(1,2,3-dithiazole), dichloro-(BB-123-DTA)(Cl), which can be reduced to neutral dichloro-(BB-123-DTA) with triphenylantimony. A similar condensation with selenium tetrachloride leads, upon reduction, to the corresponding bis(1,2,3-thiaselenazole) dichloro-(BB-123-TSA). The crystal and molecular structures of both compounds have been determined by X-ray diffraction. Both compounds, which are formally antiaromatic 16﷿-systems, exhibit internal bond lengths consistent with a quinoid formulation. The radical cations of both rings have been characterized by ESR spectroscopy; for dichloro-(BB-123-DTA) + g ) 2.0114 and aN ) 0.201 mT, while for dichloro-(BB-123-TSA) + g ) 2.021 and aN ) 0.44 mT. Further oxidation of both rings affords the corresponding dications, both of which have been characterized crystallographically as their AlCl 4 - salts. The structural features of these compounds are consistent with those expected for dithiazolylium (or thiaselenazolylium) derivatives. The structure and redox chemistry of the benzo(1,2-d:4,5-d')bis(1,2,3-dithiazole) framework is discussed in the light of the results of ab initio calculations.

The synthesis of dicyanooligothiophenes NC(C4H2S)nCN (n = 3−6) is reported. For n = 3, 4, and 5 the dinitriles are generated by treatment of the corresponding dibromo compounds with copper(I) cyanide in quinoline. For n = 6 the preparation involves the Ni-catalyzed coupling of 5-bromo-2,2‘:5‘,2‘‘-terthiophene-5‘‘-carbonitrile. The structures of all four dicyano derivatives have been determined by X-ray crystallography. For n = 3, the space group is monoclinic C2/c, with a = 18.363(7), b = 11.8356(9), c = 30.666(4) A, β = 102.15(2)°, V = 6515(3) A3, Z = 20. For n = 4 the space group is triclinic P1, a = 7.3254(9), b = 7.8658(6), c = 8.1813(8) A, α = 64.706(8), β = 76.059(8), γ = 76.692(8)°, V = 409.29(7) A3, Z = 1. For n = 5 the space group is monoclinic C2/c, with a = 13.633(4), b = 11.706(5), c = 37.073(8) A, β = 90.22(2)°, V = 5929(3) A3, Z = 12. For n = 6, the space group is monoclinic P21/a, with a = 13.8962(14), b = 5.9100(16), c = 14.0798(16) A, β = 98.446(4)°, V = 1143.8(4) A3, Z = 2. In all four ...

The title compound [CpRu(PPh3)2(tht)]BF4,1, tht=tetrahydrothiophene, is obtained by the reaction of CpRu(PPh3)2Cl, tht and AgBF4 in CH2Cl2 solution. Yellow crystals of [CpRu(PPh3)2(tht)]BF4 were grown by the slow diffusion of pentane into a CH2Cl2 solution of1 and have been studied by X-ray crystallography: space group is P21/n,a=9.507(2),b=18.336(3),c=22.372(6) A, β=94.28(2)°,V=3889(1) A3,Z=4. The tht ligand binds to the Ru atom through the sulfur atom at a distance of 2.395(2) A. The tht ring is in the puckered configuration.

The title systems have been investigated on samples quenched at 700, 800 and 1000 °C. Five new compounds have been obtained and characterized by X-ray powder diffraction: Spinel type MgGa0.2Cr1.8S4, two compounds crystallizing in the olivine structure, MgGaCrS4 and MgGaInS4, and two layered materials, MgGa1.5Cr0.5S4 and MgGa1.5In0.5S4. Lattice para­ meters and phase widths of the compounds are given.

The preparation of the bis(1,2,3,5-dithiadiazolyl) radicals [S2N2C]−X−[CN2S2], where X is a heterocyclic bridging group (X = piperazine, thiophene, bithiophene) is described. Crystal structures of ...

Cosublimation of 2,5-furanbis(1,2,3,5-dithiadiazolyl) [F-2,5-S] and iodine affords 1:1 and 2:1 charge-transfer salts, [F-2,5-S][I] and [F-2,5-S]2[I]. Cosublimation of 2,6-pyridinebis(1,2,3,5-dithiadiazolyl) [P-2,6-S] and iodine affords uniquely the 2:1 charge-transfer salt [P-2,6-S]2[I]. Crystals of the latter belong to the space group P21/c, a = 3.434(3), b = 9.8914(9), c = 30.803(4) A, β = 91.52(3)°, V = 1045.9(9) A3, Z = 2. The structure consists of [P-2,6-S] molecules stacked along the x direction. Pairs of stacks are linked head-on through iodine atoms, which themselves form disordered stacks running parallel to x. The internal structural parameters of the two CN2S2 rings within each molecule suggest that one (linked to iodine) is formally uncharged, while the other is partially oxidized. This latter ring is heavily coordinated through S- - -N linkages to neighboring CN2S2 rings and pyridine. Magnetic susceptibility measurements on [P-2,6-S]2[I] indicate that it is diamagnetic below 220 K.

The structure of the [CpRu(PPh3)2(C6H11SH)]BF4·CH2Cl2 complex was determined by X-ray diffraction techniques; triclinic space group $$P\bar 1$$ ,a=12.567(1),b=13.409(1),c=14.733(1) A, α=95.380(7), β=111.041(7), γ=96.454(8)°,V=2278.5(4) A3,Z=2,R=0.056,R w=0.088. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the S atom of the cyclohexylthiol. The Ru−S distance is 2.389(2) A and the S−H distance is 1.23 A.

A content analysis looked at 650 Internet mail messages sent to NBC Nightly News in response to an invitation during a series dealing with the impact of new technologies. Message indexes were created to reflect the scope of the audience they addressed. Macro-scopic messages were formal, dealt with political issues, and either did not mention technology or mentioned mass media. These messages resembled a letter to a newspaper editor. Mezzoscopic messages were positive and avoided political issues. They congratulated NBC as a team for their work on the technology series and tended to mention computers. Micro-scopic messages stood out for their authors' high perception of interactivity. These messages mentioned computer technology more than any other group and appear similar to face-to-face communication in many ways. Results are discussed in terms of how the relationship between media users' perceived sense of interactivity and the scope of the audience they address are related to message style and content.

Synthesis and spectroscopy of four heterobimetallic compounds containing the metal centres Cu(II)-Pd(II) and Cu(II)-Pt(II) with the multidentate nitrogen donor ligand hexakis (3,5-dimethyl-pyrazolyl)cyclotriphosphazene, (HPCTP) are reported. The complexes HPCTP·CuCl2·MX2 (M = Pd, X = Cl (3) or Br (4) and M = Pt, X = Cl (5) or Br (6)) were obtained by treating the metal-containing ligands HPCTP°CuX2 X = Cl(l) or Br(2)) with M(PhCN)2Cl2(M = Pd or Pt). The electronic absorption spectra and electron paramagnetic resonance data indicate the copper in these compounds has a distorted trigonal bipyramidal geometry. A single crystal X-ray determination of 4 is reported. The crystals of 4 are monoclinic with a = 10.570(2), b = 28.863(4), c = 16.009(1)A, β = 98.71(2)°, V = 4827(1)A3, Z = 4, D c = 1.65 g cm−3 and space group P21/c. The geometry about copper is trigonal bipyramidal with mean distances of Cu-N(pz) = 1.987(13), Cu-N(ctp) = 2.352(11) and Cu-Cl = 2.315(10)A while that of palladium is square plana...

The mixed valence compound Ga1.93V0.97S4 has been prepared and characterized by X-ray powder methods. The compound crystallizes in an α-FeGa2S4 structure. The lattice parameters of the hexagonal cell are a = 363.6 and c = 1207.1 pm. The structure has been refined by Rietveld methods.

Increasing net patient revenues from teaching clinics is one of the alternatives available to dental schools seeking to alleviate economic pressures. Managerial decisions directed to this end require accurate and useful data on clinic finances and economic organization. An important step in this direction can be taken by defining the teaching clinic as a cost center, that is as an economic entity in a dental school with identifiable specific resources, costs, and revenues. This paper describes the accounting and economics frameworks within which resources and costs are classified and allocated into direct and indirect, and fixed and variable categories. The development and structure of a cost-revenue model designed for the teaching clinics at the University of Connecticut School of Dental Medicine is described to illustrate an application of the cost center concept.

The isolation and characterization of the trimethylenesulfide-coordinated complex, [CpRu(PPh3)2(SC3H6)]CF3SO3, is reported. The structure of [CpRu(PPh3)2(SC3H6)]CF3SO3 was determined by X-ray diffraction techniques: monoclinic space group I2/a, a=23.864(10), b=14.233(3), c=24.385(7) A, β=97.10(3)°, Z=8, R=0.046, Rw=0.065. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the trimethylenesulfide. The Ru-S distance is 2.3459(20) A.

4-CF3—C6H4—CN3S2, 1, forms symmetrical sulfur-bound adducts with norbornene (NBE), norbornadiene (NBD), and 1-heptene (C7H14), which were studied by 1H, 13C, COSY-45, and HETCORR NMR. 1•NBE exists in solution in a single isomeric form which corresponds to that found in the solid state for 4-CH3O—C6H4—CN3S2•NBE by single-crystal X-ray diffraction: orthorhombic, P212121 with Z = 4, a = 10.224(3), b = 10.369(5), c = 14.075(5). R = 0.0475 and Rw = 0.0492 for 634 data. 1•NBD exists in solution in two isomeric forms which are not interchangeable. One of these corresponds to that found in the NBE adduct, i.e. exo addition; the other is the first example of endo addition. Two bis adducts of stoichiometry NBD•21 have been prepared and separated. They are isomers exhibiting exo-exo and exo-endo addition. The structure of the latter was confirmed by X-ray diffraction: orthorhombic, Pcab with Z = 8, a = 7.816(2), b = 17.264(3), c = 36.842(5). R = 0.068 and Rw = 0.106 for 1506 data. 1•C7H14 exists as a mixture of syn and anti isomers. NMR structure parameters derived here have been applied to published data on over 15 thiazene NBE and NBD adducts.

A new organic molecular conductor, based on a spiro-biphenalenyl neutral radical, simultaneously exhibits bistability in three physical channels: electrical, optical, and magnetic. In the paramagnetic state, the unpaired electrons are located in the exterior phenalenyl units of the dimer, whereas in the diamagnetic state the electrons migrate to the interior phenalenyl units and spin pair as a π-dimer. Against all expectations, the conductivity increases by two orders of magnitude in the diamagnetic state, and the band gap decreases. This type of multifunctional material has the potential to be used as the basis for new types of electronic devices, where multiple physical channels are used for writing, reading, and transferring information.

In the quasibinary system MnIn 2 S 4 -MnIn 2 Se 4 a series of solid solutions of general formula MnIn 2 S x Se 4- x exists for 2.4 ≥ x ≥ 0.2 with the layered MgAl 2 S 4 structure. The samples have been characterized by X-ray powder diffraction and investigated by electrical measurements and diffuse reflectance spectroscopy. The compounds are semiconductors with optical band gaps varying between 1.6 and 1.2 eV depending on x . From Arrhenius plots of the conductivity data at least two different activation energies E a can be obtained: in the temperature interval from 50 to 200°C we find E a = 0.5 eV, independent of the composition of the samples, while in the high temperature region from 200 to 400°C, E a varies with x from 1.35 to 0.56 eV.

The structure of the [CpRu(PPh[sub 3])[sub 2](t[minus]C[sub 4]H[sub 4]SH)]BF[sub 4] complex was determined by X-ray diffraction techniques; monoclinic space group P2[sub 1]/c, a = 14.662(9), b = 18.515(7), c = 15.368(6) [angstrom], [beta] = 101.88(5)[degrees], V = 4082(6) [angstrom][sup 3], Z = 4, R = 0.049, R[sub w] = 0.057. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the t-butylmercaptan. The Ru-S distance is 2.396(2)[angstrom] and the S-H distance is 1.289(2)[angstrom].

The reactions of N,N,N[prime]-tris(trimethylsilyl)formamidine with ECl[sub 2] (E = S, Se) afford 1,2,3,5-dithia- and 1,2,3,5-diselenadiazolium chloride, which can be reduced with triphenylantimony to the corresponding dithia- and diselenadiazolyl radicals [HCN[sub 2]E[sub 2]]. The solid state structure of the cofacial dimer [HCN[sub 2]S[sub 2]][sub 2] has been determined by X-ray diffraction; crystals of [HCN[sub 2]S[sub 2]][sub 2] belong to the monoclinic space group P2[sub 1]/n, with a = 6.833(6), b = 16.463(4), c = 19.161(4) A, [beta] = 93.57(4)[degrees], FW = 210.30, Z = 12. The crystal structure consists of stacked dimers, with three dimers in the asymmetric unit. Along the stacking axis the mean intradimer S---S contact is 3.11 A; the mean interdimer contact is 3.76 A. Ab initio calculations with split-valence and larger basis sets have been employed to evaluate the structures and energies of both the gas phase radicals and their dimers. Minor changes in geometry are predicted upon association of the monomers; this relative structural invariance is consistent with low binding energies, the best predictions (including zero point vibrational energy corrections) being ca. 4 kcal/mol (for E = S) and ca. 10 kcal/mol (for E = Se). 30 refs., 6 figs., 9 tabs.

The preparation and solid-state characterization of the 1,3,5-triazine-bridged tris(1,2,3,5-ditliiadiazolyl) complex 4,4',4''-(2,4,6-(1,3,5-triazinetriyl))tris(1,2,3,5-dithiadiazolyl) [N 3 C 3 (CN 2 S 2 ) 3 ] are described. The crystals belong to the monoclinic space group C2/c, with a=20.759(7) A, b=10.525(3) A, c=17.554(3) A, β=140.18(4) o , fw=390.5, Z=8, and V=2456.2(12) A 3 . The crystal structure consists of layers of interlocked dimers. Alternate layers are oriented in an antiparallel fashion, thereby precluding a stacked structure similar to that found in the related 1,3,5-benzene-based triradical. There are two dimerization environments

The reaction of [CpRu(PPh3)2(n-C3H7SH)]BF4 with dithiooxamide (dtoxa) gave two products: {[CpRu(PPh3)2]2(μ-dtoxa)} (BF4)2,1, and [CpRu(PPh3)(dtoxa-H2O)]BF4,2. The structures of both complexes were determined by X-ray diffraction techniques. Compound1 crystallized in the triclinic space groupP¯1,a=12.822(4),b=14.16(1),c=23.631(8) A,α=84.57(4),β=83.64(3), γ=83.57(4)°,Z=2,R=0.069,Rw=0.084. The structure of1 shows two CpRu(PPh3)2+ units bridged through the S atoms of the dtoxa ligand. Ru-S distances are 2.377(6)A for Ru1-S1 and 2.368(6) A for Ru2-S2. Compound2 crystallized in the monoclinic space groupP21/c,a=13.446(3),b=13.461(7),c=31.214(7) A,β=100.78(3)°,Z=8,R=0.054,Rw=0.055. The structure of2 has two molecules in the asymmetric unit. The Ru is chelated to the dtoxa through the S atoms: Ru1-S1, 2.307(4); Ru1-S2, 2.300(4); Ru2-S3, 2.295(4); Ru2-S4, 2.287(4) A. The coordination sphere of the Ru in2 is completed by a cyclopentadienyl ligand and a triphenylphosphine.

The reactions of hexakis(3,5-dimethylpyrazolyl)cyclotriphosphazene, N 3 P 3 (3,5-Me 2 Pz) 6 (HPCTP) (3), with copper-(II) halides afford mononuclear HPCTP.CuX 2 (X=Cl, 3a; X=Br, 3b) and dinuclear HPCTP.2CuX 2 (X=Cl, 3c; X=Br, 3d) coordination complexes. Optical absorption spectra and ESR spectra of these complexes; the structure or HPCTP-CuCl 2 was determined by X-ray crystallography.

The isolation and characterization of two mercaptan complexes of the general formula [CpRu(PPh3)2(RSH)]BF4, where R=benzyl and phenethyl, were undertaken to model the substrate/catalyst interaction of the hydrode-sulfurization (HDS) process. The IR data show a shift in the SH stretching frequency upon coordination. The structure of the [CpRu(PPh3)2(C6H5CH2CH2SH)]BF4 complex was determined by X-ray diffraction techniques: monoclinic space group P21/n, a=15.317(4), b=13.924(9), c=21.815(7) A, β=95.20(2)°, Z=4, R=0.057, Rw=0.073. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the phenethylmercaptan. The Ru-S distance is 2.369(2) A and the S-H distance is 1.18 A.