Interdependence of redox state,hydrogen bonding,anion recognition and charge partition in crystals of (EDT-TTF-CONHMe)6 [Re6Se8(CN)6] (CH3CN)2(CH2Cl2)2

Neutral pi-conjugated molecules and their radical cations co-exist in [(EDT-TTF-CONHMe+*)4(EDT-TTF-CONHMe0)2] [Re6Se8(CN)6]4- (CH3CN)2(CH2Cl2)2 whose crystal structure reveals that, upon one-electron oxidation, an activation of the N-H and C-H hydrogen bond donor ability is coupled to a deactivation of the hydrogen bond acceptor character of the carbonyl oxygen atom: this is expressed in the supramolecular hydrogen bond pattern and, ultimately, into charge localisation and partition in the solid state.     

Modulating the framework negative charge density in the system [BDT-TTP*+]/[Re6S5Cl9(1-)]/[Re6(S/Se)6Cl8(2-)]/[Re6S7Cl7(3-)]: templating by isosteric cluster anions of identical symmetry and shape, variations of incommensurate band filling, and electronic structure in 2D metals

A series of 2D metals, beta-(BDT-TTP)6[Re6Se6Cl8] x (CHCl2-CHCl2)2, 2; beta-(ST-TTP)6[Re6S6Cl8] x (CH2Cl-CHCl2)2, 3; beta-(BDT-TTP)7[Re6S6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 4; beta-(BDT-TTP)7[Re6Se6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 5; beta-(BDT-TTP)8[Re6S7Cl7] x (CH2Cl2)4, 6 (BDT-TTP and ST-TTP are 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene and 2-(1,3-diselenol-2-ylidene)-5(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene, respectively) is reported to have one single beta-slab layered topology despite successive increases of the cluster anion negative charge. The charge density within the templating composite inorganic-neutral molecule slab is shown to remain above a threshold of ca. one negative charge per square nanometer, that is, for cluster anions with two negative charges and higher. Conversely, discrete stacks are shown to be stabilized instead in the semiconducting salts (BDT-TTP)2[Re6S5Cl9], 1 where the cluster anion bears one negative charge only. The electronic structure of salts 2-6 is shown to be very stable and kept almost intact across the series. The templating strategy is shown to fulfill its anticipated potential for deliberate installment of incommensurate band fillings in molecular metals. The deliberate admixture of the 6:1 and 8:1 structures yields novel phases with a 7:1 stoichiometry with the anticipated crystal and electronic structures. The action at the organic-inorganic interface triggered by changing the anion charge yet keeping its shape and volume identical, which ultimately governs the shape of the unit cell, is of paramount importance in defining the Fermi surface of these metallic salts. The present BDT-TTP salts thus provide a series of materials with strongly related but subtly different Fermi surfaces worthy of many physical studies. Shubnikov-de Haas measurements are expected to be particularly interesting since they are especially sensitive to the details of the Fermi surface.     

Cluster-to-metal magnetic coupling: synthesis and characterization of 25-electron [Re6-nOsnSe8(CN)6](5-n)-(n = 1, 2) clusters and (Re6-nOsnSe8[CNCu(Me6tren)]6)9+(n = 0, 1, 2) assemblies

The first face-capped octahedral clusters with 25 metal-based valence electrons are shown to provide versatile building units capable of engaging in magnetic exchange coupling. Reactions of [Re(5)OsSe(8)Cl(6)](3-) and [Re(4)Os(2)Se(8)Cl(6)](2-) with NaCN in a melt of NaNO(3) or KCF(3)SO(3) afford the 24-electron clusters [Re(5)OsSe(8)(CN)(6)](3-) and [Re(4)Os(2)Se(8)(CN)(6)](2-). The 13C NMR spectrum of a 13C-labeled version of the latter species indicates a 1:2 mixture of cis and trans isomers. Cyclic voltammograms of the clusters in acetonitrile display reversible [Re(5)OsSe(8)(CN)(6)](3-/4-), cis-[Re(4)Os(2)Se(8)(CN)(6)](2-/3-), and trans-[Re(4)Os(2)Se(8)(CN)(6)](2-/3-) couples at E(1/2) = -1.843, -0.760, and -1.031 V vs FeCp(2)(0/+), respectively, in addition to other redox processes. Accordingly, reduction of [Re(5)OsSe(8)(CN)(6)](3-) with sodium amalgam and [Re(4)Os(2)Se(8)(CN)(6)](2-) with cobaltocene produces the 25-electron clusters [Re(5)OsSe(8)(CN)(6)](4-) and [Re(4)Os(2)Se(8)(CN)(6)](3-). EPR spectra of these S = 1/2 species in frozen DMF solutions exhibit isotropic signals with g = 1.46 for the monoosmium cluster and g = 1.74 and 1.09 for the respective cis and trans isomers of the diosmium cluster. In each case, results from DFT calculations show the unpaired spin to delocalize to some extent into the pi* orbitals of the cyanide ligands, suggesting the possibility of magnetic superexchange. Reaction of [Re(5)OsSe(8)(CN)(6)](3-) with [Ni(H(2)O)(6)](2+) in aqueous solution generates the porous Prussian blue analogue Ni(3)[Re(5)OsSe(8)(CN)(6)](2).32H(2)O; however, the tendency of the 25-electron clusters to oxidize in water prohibits their use in reactions of this type. Instead, a series of cyano-bridged assemblies, [Re(6-n)Os(n)Se(8)[CNCu(Me(6)tren)](6)](9+) (n = 0, 1, 2; Me(6)tren = tris(2-(dimethylamino)ethyl)amine), were synthesized to permit comparison of the exchange coupling abilities of clusters with 23-25 electrons. As expected, the results of magnetic susceptibility measurements show no evidence for exchange coupling in the assemblies containing the 23- and 24-electron clusters, but reveal the presence of weak ferromagnetic coupling in [Re(4)Os(2)Se(8)[CNCu(Me(6)tren)](6)](9+). Assuming all cluster-Cu(II) exchange interactions to be equivalent, the data were fit to give an estimated coupling strength of J = 0.4 cm(-1). To our knowledge, the ability of such clusters to participate in magnetic exchange coupling has never previously been demonstrated.     

Symmetry-breaking substitutions of [Re(CN)8]3- into the centered, face-capped octahedral clusters (CH3OH)24M9M'6(CN)48 (M = Mn, Co; M = Mo, W)

The diamagnetic complex [Re(CN)8]3- is shown to react with Mn2+ ions in methanol to generate the centered, face-capped octahedral cluster (CH3OH)24Mn9Re6(CN)48, which is structurally analogous to (CH3OH)24Mn9Mo6(CN)48. Related reactions involving stoichiometric mixtures of octacyanometalate complexes generate the substituted species (CH3OH)24Mn9Mo5Re(CN)48, (CH3OH)24Co9Mo5Re(CN)48, (CH3OH)24Mn9Mo3Re3(CN)48, (CH3OH)24Mn9W5Re(CN)48 and (CH3OH)24Co9W5Re(CN)48, in which the O(h) symmetry of the cluster core is broken. Reassessment of the magnetic properties of the Mn9Mo6(CN)48 cluster confirm that it possesses a ground state spin of S = 39/2, but does not exhibit single-molecule-magnet behavior. Lowering the symmetry of the molecule by substitutions of ReV at one or three of the MoV sites does not lead to an overall increase in the magnetic anisotropy, as probed by ac magnetic susceptibility measurements. A similar result occurs for the other substituted species, with the important exception of the new single-molecule magnet (CH3OH)24Co9W5Re(CN)48, for which the spin reversal barrier is significantly reduced relative to that observed previously in (CH3OH)24Co9W6(CN)48.     

CRYSTAL STRUCTURE OF [Cu(NH3)2]2[{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6]

Journal of Structural Chemistry - Chain coordination polymer [Cu(NH3)2]2[{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6] (1) is obtained by a reaction of Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O with CuCN in the...     

Site-differentiated hexanuclear rhenium(III) cyanide clusters [Re(6)Se(8)(PEt(3))(n)()(CN)(6)(-)(n)()](n)()(-)(4) (n = 4, 5) and kinetics of solvate ligand exchange on the cubic [Re(6)Se(8)](2+) Core

The site-differentiated, cyanide-substituted hexanuclear rhenium(III) selenide clusters cis- and trans-[Re(6)Se(8)(PEt(3))(4)(CN)(2)] and [Re(6)Se(8)(PEt(3))(5)(CN)](+) have been prepared from heterogeneous reactions of the corresponding iodo clusters with AgCN in refluxing chloroform. Isolated yields are 68%, 46%, and 64% for cis-[Re(6)Se(8)(PEt(3))(4)(CN)(2)], trans-[Re(6)Se(8)(PEt(3))(4)(CN)(2)], and [Re(6)Se(8)(PEt(3))(5)(CN)](+), respectively. The new compounds are air- and water-stable and are characterized by X-ray diffraction crystallography, (31)P NMR and IR spectroscopies, and FAB mass spectrometry. In related work, the solvent exchange rates of two site-differentiated monosolvate clusters, [Re(6)Se(8)(PEt(3))(5)(MeCN)](SbF(6))(2) and [Re(6)Se(8)(PEt(3))(5)(Me(2)SO)](SbF(6))(2), in neat solvents were measured by (1)H NMR. These clusters are substitutionally inert; k approximately 10(-)(5)-10(-)(6) s(-)(1) at 318 K. Activation parameters indicate a dissociative ligand exchange mechanism; DeltaH() values obtained from least-squares fitting of temperature-dependent kinetics data exceed RT by a factor of ca. 50 over the temperature range studied. These results demonstrate that the substitutional lability encountered in a previous study of cluster photophysics (Gray, T. G.; Rudzinski, C. M.; Nocera, D. G.; Holm, R. H. Inorg. Chem. 1999, 38, 5932) cannot result from ground-state thermal reactions.     

Determination of 77Se-77Se and 77Se-13C J-coupling parameters for the clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2-

We have investigated rarely observed 77Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between mu3-Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re4Os2Se8(CN)6]2- were distinguishable, and selective isotopic labeling of [Re5OsSe8(CN)6]3- with 13CN ligands enabled resonances to be assigned by observing the 2J (Se-M-C) couplings. For [Re5OsSe8(CN)6]3-, two different 2J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites.     

Expanded Prussian blue analogues incorporating [Re6Se8(CN)6](3-/4-) clusters: adjusting porosity via charge balance

Face-capped octahedral [Re(6)Se(8)(CN)(6)](3-/4-) clusters are used in place of octahedral [M(CN)(6)](3-/4-) complexes for the synthesis of microporous Prussian blue type solids with adjustable porosity. The reaction between [Fe(H(2)O)(6)](3+) and [Re(6)Se(8)(CN)(6)](4-) in aqueous solution yields, upon heating, Fe(4)[Re(6)Se(8)(CN)(6)](3).36H(2)O (4). A single-crystal X-ray analysis confirms the structure of 4 to be a direct expansion of Prussian blue (Fe(4)[Fe(CN)(6)](3).14H(2)O), with [Re(6)Se(8)(CN)(6)](4-) clusters connected through octahedral Fe(3+) ions in a cubic three-dimensional framework. As in Prussian blue, one out of every four hexacyanide units is missing from the structure, creating sizable, water-filled cavities within the neutral framework. Oxidation of (Bu(4)N)(4)[Re(6)Se(8)(CN)(6)] (1) with iodine in methanol produces (Bu(4)N)(3)[Re(6)Se(8)(CN)(6)] (2), which is then metathesized to give the water-soluble salt Na(3)[Re(6)Se(8)(CN)(6)] (3). Reaction of [Co(H(2)O)(6)](2+) or [Ni(H(2)O)(6)](2+) with 3 in aqueous solution affords Co(3)[Re(6)Se(8)(CN)(6)](2).25H(2)O (5) or Ni(3)[Re(6)Se(8)(CN)(6)](2).33H(2)O (6). Powder X-ray diffraction data show these compounds to adopt structures based on the same cubic framework present in 4, but with one out of every three cluster hexacyanide units missing as a consequence of charge balance. In contrast, reaction of [Ga(H(2)O)(6)](3+) with 3 gives Ga[Re(6)Se(8)(CN)(6)].6H(2)O (7), wherein charge balance dictates a fully occupied cubic framework enclosing much smaller cavities. The expanded Prussian blue analogues 4-7 can be fully dehydrated, and retain their crystallinity with extended heating at 250 degrees C. Consistent with the trend in the frequency of framework vacancies, dinitrogen sorption isotherms show porosity to increase along the series of representative compounds 7, Ga(4)[Re(6)Se(8)(CN)(6)](3).38H(2)O, and 6. Furthermore, all of these phases display a significantly higher sorption capacity and surface area than observed in dehydrated Prussian blue. Despite incorporating paramagnetic [Re(6)Se(8)(CN)(6)](3-) clusters, no evidence for magnetic ordering in compound 6 is apparent at temperatures down to 5 K. Reactions related to those employed in preparing compounds 4-6, but carried out at lower pH, produce the isostructural phases H[cis-M(H(2)O)(2)][Re(6)Se(8)(CN)(6)].2H(2)O (M = Fe (8), Co (9), Ni (10)). The crystal structure of 8 reveals a densely packed three-dimensional framework in which [Re(6)Se(8)(CN)(6)](4-) clusters are interlinked through a combination of protons and Fe(3+) ions.     

Structural and functional characteristics of rhenium clusters derived from redox chemistry of the triangular [ReIII3(mu-Cl)3] core unit

The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3(8+) core. Dissolution of 1 in HCl (6 M) generates [Re3(mu-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6-12 M) produces [(C6H5)4P]2[Re3(mu-Cl)3Cl7(H2O)2].H2O (3), the structure of which features a planar [Re3(mu-Cl)3Cl3] framework (Re3(8+) core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3(8+)-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-OH))2].2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3(9+) triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-Cl))2].10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1-3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(mu-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(mu-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(mu-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3(8+) cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(mu-Cl)3Cl7(CH3C(O)NH)].CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(mu-Cl)3Cl8(MeOH)].MeOH (10).     

Conversion of a Re(IV) tetrahedral cluster to a Re(III) octahedral cluster: synthesis of [(CH3)C(NH2)(2)](4)[Re(6)Se(8)(CN)(6)] by a solvothermal route

The compound [(CH(3))C(NH(2))(2)](4)[Re(6)Se(8)(CN)(6)] has been synthesized by the reaction at 200 degrees C for 3 days of Re(4)Te(4)(TeCl(2))(4)Cl(8), KSeCN, and NH(4)Cl in superheated acetonitrile. This compound crystallizes in the space group C2/c of the monoclinic system with four formula units in a cell of dimensions a = 20.3113(14) A, b = 10.1332(7) A, c = 19.9981(14) A, beta = 106.754(1) degrees, V = 3941.3(5) A(3) (T = 153 K). The [Re(6)Se(8)(CN)(6)](4-) anion comprises an Re(6) octahedron face capped by mu(3)-Se atoms, with each Re atom liganded by a CN group. The anions and cations are connected by an extensive network of hydrogen bonds. The conversion of a Re(IV) tetrahedral cluster to a Re(III) octahedral cluster appears to be unprecedented.     

Preparation of a family of hexanuclear rhenium cluster complexes containing 5-(phenyl)tetrazol-2-yl ligands and alkylation of 5-substituted tetrazolate ligands

The preparation of two new families of hexanuclear rhenium cluster complexes containing benzonitrile and phenyl-substituted tetrazolate ligands is described. Specifically, we report the preparation of a series of cluster complexes with the formula [Re(6)Se(8)(PEt(3))(5)L](2+) where L = benzonitrile, p-aminobenzonitrile, p-methoxybenzonitrile, p-acetylbenzonitrile, or p-nitrobenzonitrile. All of these complexes undergo a [2 + 3] cycloaddition with N(3)(-) to generate the corresponding [Re(6)Se(8)(PEt(3))(5)(5-(p-X-phenyl)tetrazol-2-yl)](+) (or [Re(6)Se(8)(PEt(3))(5)(2,5-p-X-phenyltetrazolate)](+)) cluster complexes, where X = NH(2), OMe, H, COCH(3), or NO(2). Crystal structure data are reported for three compounds: [Re(6)Se(8)(PEt(3))(5)(p-acetylbenzonitrile)](BF(4))(2)?MeCN, [Re(6)Se(8)(PEt(3))(5)(2,5-phenyltetrazolate)](BF(4))?CH(2)Cl(2), and [Re(6)Se(8)(PEt(3))(5)(2,5-p-aminophenyltetrazolate)](BF(4)). Treatment of [Re(6)Se(8)(PEt(3))(5)(2,5-phenyltetrazolate)](BF(4)) with HBF(4) in CD(3)CN at 100 °C leads to protonation of the tetrazolate ring and formation of [Re(6)Se(8)(PEt(3))(5)(CD(3)CN)](2+). Surprisingly, alkylation of the phenyl and methyl tetrazolate complexes ([Re(6)Se(8)(PEt(3))(5)(2,5-N(4)CPh)](BF(4)) and [Re(6)Se(8)(PEt(3))(5)(1,5-N(4)CMe)](BF(4))) with methyl iodide and benzyl bromide, leads to the formation of mixtures of 1,5- and 2,5-disubstituted tetrazoles.     

Re6Te8(CN)6][(Ir(CO)(PPh3)2)6](OTf)2 : a new Re6 cluster-supported iridium(I) compound

A new hexanuclear rhenium cluster encapsulated by six iridium complexes, [Re6Te8(CN)6][(Ir(CO)(PPh3)2)6](OTf)2 (3), which is effective in catalyzing the hydrogenation of p-CH3C6H4C[triple bond]CH to p-CH3C6H4CH=CH2 has been prepared.     

New linear tricobalt complex of di(2-pyridyl)amide (dpa), [Co3(dpa)4(CH3CN)2][PF6]2

Reaction of the linear tricobalt compound Co3(dpa)4Cl2 (1) (dpa = di(2-pyridyl)amide) with silver hexafluorophosphate in acetonitrile yields [Co3(dpa)4(CH3CN)2][PF6]2 (2). Two crystalline forms are obtained from the same solution, namely, a monoclinic (P2(1)) form 2xCH3CNx2Et2O and a triclinic (P1) form, 2x3CH3CN. The tricobalt units in both crystals are essentially symmetrical, though this is not required by crystal symmetry, with Co-Co distances in the range 2298-2304 A. Each of the two terminal Co atoms is coordinated to an acetonitrile molecule with Co-N distances in the range 2068-2111 A at 213 K. The spiral arrangement of ligands gives an overall idealized D4 point group symmetry for the cation [Co3(dpa)4(CH3CN)2]2+ . Chiral crystals of both delta and lambda configurations in the P2(1) form have been isolated. The absolute configurations were determined by X-ray crystallography and their mirror-image circular dichroism spectra measured. The D4 symmetry of the cation appears to be preserved in solution as judged by the presence of only five proton resonance signals in the 1H NMR spectrum. Magnetic susceptibility measurements in the solid state indicates that 2 has a doublet ground state and exhibits an increase of the effective moment at high temperature (approximately 160 K) due to a spin crossover process.     

A family of octahedral rhenium cluster complexes [Re6Q8(H2O)n(OH)6-n]n-4 (Q=S, Se; n=0-6): structural and pH-dependent spectroscopic studies

The conversions of hexahydroxo rhenium cluster complexes [Re6Q8(OH)6]4- (Q=S, Se) in aqueous solutions in a wide pH range were investigated by chemical methods and spectroscopic measurements. Dependences of the spectroscopic and excited-state properties of the solutions on pH have been studied in detail. It has been found that a pH decrease of aqueous solutions of the potassium salts K4[Re6Q8(OH)6].8H2O (Q=S, Se) results in the formation of aquahydroxo and hexaaqua cluster complexes with the general formula [Re6Q8(H2O)n(OH)6-n]n-4 that could be considered as a result of the protonation of the terminal OH- ligands in the hexahydroxo complexes. The compounds K2[Re6S8(H2O)2(OH)4].2H2O (1), [Re6S8(H2O)4(OH)2].12H2O (2), [Re6S8(H2O)6][Re6S6Br8].10H2O (3), and [Re6Se8(H2O)4(OH)2] (4) have been isolated and characterized by X-ray single-crystal diffraction and elemental analyses and infrared (IR) spectroscopy. In crystal structures of the aquahydroxo complexes, the cluster units are connected to each other by an extensive system of very strong hydrogen bonds between terminal ligands.     

Alcohol addition to acetonitrile activated by the [Re6(mu3-Se)8]2+ cluster core

The addition of methanol and ethanol to the previously reported cluster solvates [Re6(mu3-Se)8(PEt3)5(MeCN)](SbF6)2 and trans-[Re6(mu3-Se)8(PEt3)4(CH3CN)2][SbF6]2 afforded three cluster complexes with imino ester ligands: {Re6(mu3-Se)8(PEt3)5[HN=C(OCH3)(CH3)]}(SbF6)2, {Re6(mu3-Se)8(PEt3)5[HN=C(OCH2CH3)(CH3)]}{SbF6}2, and trans-{Re6(mu3-Se)8(PEt3)4[HN=C(OCH3)(CH3)]2}{SbF6}2. In all cases, predominant formation of the Z isomers was observed.     

Diorganodiselenides and zinc(II) organoselenolates containing (imino)aryl groups of type 2-(RN=CH)C6H4

Several new diorganodiselenides containing (imino)aryl groups, [2-(RN[double bond, length as m-dash]CH)C(6)H(4)](2)Se(2) [R = Me(2)NCH(2)CH(2) (4), O(CH(2)CH(2))(2)NCH(2)CH(2) (5), PhCH(2) (6), 2',6'-(i)Pr(2)C(6)H(3) (7)] were obtained by reacting [2-{(O)CH}C(6)H(4)](2)Se(2) (3) with RNH(2). Treatment of the diselenides 6 and 7 with stoichiometric amounts of K-selectride or Na resulted in isolation of the selenolates K[SeC(6)H(4)(CH[double bond, length as m-dash]NCH(2)Ph)-2] (9) and Na[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2] (10), respectively. The reaction of potassium selenolates with anhydrous ZnCl(2) (2:1 molar ratio) gave Zn[SeC(6)H(4)(CH=NCH(2)Ph)-2](2) (11) and Zn[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2](2) (12). When the dark green solution obtained from diselenide 7 and an excess of Na (after removal of the unreacted metal) was reacted with anhydrous ZnCl(2) a carbon-carbon coupling reaction occurred and the 9,10-(2',6'-(i)Pr(2)C(6)H(3)NH)(2)C(14)H(10) (8) species was obtained. The compounds were investigated in solution by multinuclear NMR ((1)H, (13)C, (77)Se, including 2D and variable temperature experiments) and by mass spectrometry. The molecular structures of 6, 8, 11 and 12 were established by single-crystal X-ray diffraction. All compounds are monomeric in the solid state. In the diselenide 6 the (imino)aryl group acts as a (C,N)-ligand resulting in a distorted T-shaped coordination geometry of type (C,N)SeX (X = Se). For the zinc complexes 11 and 12 the (Se,N) chelate pattern of the selenolato ligands results in tetrahedral Zn(Se,N)(2) cores.     

An in-depth correlation of perturbation of the organic-inorganic interface topology,electronic structure,and transport properties within beta''-(BEDT-TTF)(4) x (guest)(n) x [Re(6)Q(6)Cl(8)], (Q=S,Se)

An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, beta'-(BEDT-TTF)(4) x (guest)(n) x [Re(6)Q(6)Cl(8)], (BEDT-TTF=bis-ethylenedithiotetrathiafulvalene; Q = S, Se; guest = H(2)O, 1,4-dioxane, THF, CCl(4), C(2)H(5)OH, CHCl(3), CH(2)ClI, CH(2)ClBr, CH(2)Cl(2), CH(2)OH-CH(2)OH, C(5)H(5)N, CH(3)COCH(3), 2-hydroxy-tetrahydrofuran, CH(3)CN, CS(2), C(6)H(6)), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H...Cl-mu-Re, (C-H)(BEDT-TTF)...Cl-mu-Re, C-H...O(guest), (C-H)(guest)...Cl-mu-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the pi-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.     

Octacyanometallate-based single-molecule magnets: Co(II)9M(V)6 (M = W, Mo)

Two octacyanometallate-based clusters, {CoII9[WV(CN)8]6.(CH3OH)24}.19H2O (1) and {CoII9[MoV(CN)8]6.(CH3OH)24}.4CH3OH.16H2O (2), have been synthesized. Both complexes show the single-molecule magnet behavior.     

Preparation,structures, and redox and emission characteristics of the isothiocyanate complexes of hexarhenium(III) clusters [Re6(mu3-E)8(NCS)6]4- (E = S,Se)

Hexarhenium(III) complexes with terminal isothiocyanate ligands, [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)(NCS)(6)] (1) and (L)(4)[Re(6)(mu(3)-Se)(8)(NCS)(6)] (L(+) = PPN(+) (2a), (n-C(4)H(9))(4)N(+) (2b)), have been prepared by three different methods. Complex 1 was prepared by the reaction of [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] with molten KSCN at 200 degrees C, while 2b was obtained by refluxing the chlorobenzene-DMF (2:1 v/v) solution of [Re(6)(mu(3)-Se)(8)(CH(3)CN)(6)](SbF(6))(2) and [(n-C(4)H(9))(4)N]SCN. The [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-) anion was also obtained from a mixture of Cs(2)[Re(6)(mu(3)-Se)(8)Br(4)] and KSCN in C(2)H(5)OH by a mechanochemical activation at room temperature for 20 h and isolated as 2a. The X-ray structures of 1 and 2a.4DMF have been determined (1, C(70)H(144)N(10)S(14)Re(6), monoclinic, space group P2(1)/n (No. 14), a = 14.464(7) A, b = 22.059(6) A, c = 16.642(8) A, beta = 113.62(3) degrees, V = 4864(3) A(3), Z = 2; 2a.4DMF, C(162)H(144)N(14)O(4)P(8)S(6)Se(8)Re(6), triclinic, space group P1 (No. 2), a = 15.263(2) A, b = 16.429(2) A, c = 17.111(3) A, alpha = 84.07(1) degrees, beta = 84.95(1) degrees, gamma = 74.21(1) degrees, V = 4098.3(8) A(3), Z = 1). All the NCS(-) ligands in both complexes are coordinated to the metal center via nitrogen site with the Re-N distances in the range of 2.07-2.13 A. The redox potentials of the reversible Re(III)(6)/Re(III)(5)Re(IV) process in acetonitrile are +0.84 and +0.70 V vs. Ag/AgCl for [Re(6)(mu(3)-S)(8)(NCS)(6)](4)(-) and [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-), respectively, which are the most positive among the known hexarhenium complexes with six terminal anionic ligands. The complexes show strong red luminescence with the emission maxima (lambda(max)/nm), lifetimes (tau(em)/micros), and quantum yields (phi(em)) being 745 and 715, 10.4 and 11.8, and 0.091 and 0.15 for 1 and 2b, respectively, in acetonitrile. The data reasonably well fit in the energy-gap plots of other hexarhenium(III) complexes. The temperature dependence of the emission spectra and tau(em) of 1 and [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] are also reported.     

SYNTHESIS AND CRYSTAL STRUCTURES OF IONIC CLUSTER COMPLEXES [Cu2(en)2(μ-CN)][{Cu(en)}3Re6Q8(CN)6]·en·H2O (Q = S,Se)

Journal of Structural Chemistry - Two new compounds of the composition [Cu2(en)2(μ-CN)][{Cu(en)}3Re6Q8(CN)6]·en·H2O (Q = S, Se) are synthesized under solvothermal...