Crystal structures and magnetic properties of (4,4'-phenylazophenyl)diammonium(crown ethers)[Ni(dmit)2]2 crystals

Sandwich-type hydrogen-bonded supramolecular dications (DAAz(2+))([18]crown-6)(2) and (DAAz(2+))(dicyclohexane[18]crown-6)(2) (DAAz(2+) = 4,4'-(phenylazophenyl)diammonium) were introduced into [Ni(dmit)(2)](-) anions via a diffusion method to form novel single crystals (DAAz(2+))([18]crown-6)(2)[Ni(dmit)(2)](2) (1) and (DAAz(2+))(dicyclohexane[18]crown-6)(2)[Ni(dmit)(2)](2) (2), respectively, which were characterized based on their crystal structures and magnetic susceptibilities. The molecular assembly structures and its physical properties were expanded in the use of a three component molecular network system. The two ammonium groups (-NH(3)(+)) of the DAAz(2+) dication formed N-H(+)-O hydrogen-bonding interactions with the oxygen atoms of [18]crown-6 and dicyclohexane[18]crown-6. In the case of crystal 1, an alternating π-stacking interaction was observed for the [Ni(dmit)(2)](-) anions, whereas orthogonal linear π-S interactions were detected for crystal 2. Temperature-dependent magnetic susceptibilities of crystals 1 and 2 followed the alternate Heisenberg antiferromagnetic chain (J = -15.8 K) and linear Heisenberg antiferromagnetic chain (J = -13.7 K) models, respectively.     

Supramolecular cation assemblies of hydrogen-bonded (NH4+/NH2NH3+)(crown ether) in [Ni(dmit)2]-based molecular conductors and magnets

Hydrogen-bonded supramolecular cation assemblies of (NH4+/NH2-NH3+)(crown ether), where the crown ether is [12]crown-4, [15]crown-5, or [18]crown-6, were incorporated into electrically conducting [Ni(dmit)2] salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate). (NH4+)([12]crown-4)[Ni(dmit)2]3(CH3CN)2 had a pyramidal shape, while ionic channels were observed in (NH4+)(0.88)([15]crown-5)[Ni(dmit)(2)]2 and (NH4+)(0.70)([18]crown-6)[Ni(dmit)(2)]2. Both (NH4+)(0.88)([15]crown-5) and (NH4+)(0.70)([18]crown-6) contained regularly spaced [Ni(dmit)(2)] stacks formed by N-H.O hydrogen bonding between the oxygen atoms in crown ethers and the NH4+ ion. NH4+ occurred nonstoichiometrically; there were vacant ionic sites in the ionic channels. The ionic radius of NH4+ is larger than the cavity radius of [15]crown-5 and [18]crown-6. Therefore, NH4+ ions could not pass through the cavity and were distributed randomly in the ionic channels. The static disorder caused the conduction electrons to be randomly localized to the [Ni(dmit)2] stacks. Hydrazinium (NH2-NH3+) formed the supramolecular cations in (NH2-NH3+)([12]crown-4)2[Ni(dmit)2]4 and (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6, possessing a sandwich and club-sandwich structure, respectively. To the best of our knowledge, these represent the first hydrazinium-crown ether assemblies to be identified in the solid. In the supramolecular cations, hydrogen bonding was detected between the ammonium or the amino protons of NH2-NH3+ and the oxygen atoms of crown ethers. The sandwich-type cations coexisted with the [Ni(dmit)2] dimer stacks. Although the assemblies were typically semiconducting, ferromagnetic interaction (Weiss temperature = +1 K) was detected in the case of (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6. The (NH2-NH3+)0.8([18]crown-6)[Ni(dmit)2]2 and (NH4+)0.76([18]crown-6)[Ni(dmit)2]2 crystals were isomorphous. The large and flexible [18]crown-6 allowed for maintaining the same ionic channel structure through replacement of the NH4+ cation by NH2-NH3+.     

Crystal structure and magnetic properties of Gd2([18]crown-6)2(OH)2(CH3CN)2[Ni(dmit)2]4 complex having f- and pi-spins

Crystal structure and magnetic properties of Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2)[Ni(dmit)(2)](2) (dmit(2)(-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) are reported. Gd(3+) ions (S = (7)/(2)) were introduced into the pi-spin network of [Ni(dmit)(2)](-) (S = (1)/(2)) complex as a binuclear supramolecular cation, Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2), in which two Gd([18]crown-6) units are bridged with two hydroxide ions. The weak antiferromagnetic interactions between Gd.Gd through hydroxide ions were observed, and [Ni(dmit)(2)](-) formed isolated monomers and dimers in the crystal.     

Supramolecular cations of the m-fluoroanilinium(dibenzo[18]crown-6) in ferromagnetic salt

A supramolecular cation of (m-FAni(+))(DB[18]crown-6), where m-FAni(+) and DB[18]crown-6 denote m-fluoroanilinium(+) and dibenzo[18]crown-6, respectively, which is the polar unit rotating in the ferroelectric crystal of (m-FAni(+))(DB[18]crown-6)[Ni(dmit)(2)](-), was introduced into a ferromagnetic [MnCr(oxalate)(3)](-) salt as the counter cation. The crystal structure of (m-FAni(+))(DB[18]crown-6)[MnCr(oxalate)(3)](-)(CH(3)OH)(CH(3)CN) (1) is constructed from alternating layers of a two-dimensional honeycomb layer of [MnCr(oxalate)(3)](-) and (m-FAni(+))(DB[18]crown-6) supramolecular cations. The anionic layer is composed of Mn(II) and Cr(III) ions with S = 5/2 and S = 3/2 spins, respectively, bridged by the oxalate anions, which show ferromagnetic ordering at 5.5 K. The supramolecular structure is formed through the formation of hydrogen bonds between the ammonium hydrogen atoms of the m-FAni(+) cations and the oxygen atoms of the DB[18]crown-6 cavity. No orientational disorder of the fluorine atoms was observed in our X-ray structural analysis, suggesting that a two-fold flip-flop motion of the m-FAni(+) cations does not occur in the salt. The rotational freedom of the m-FAni(+) cations in the salt is restricted by the steric hindrance from neighbouring DB[18]crown-6 molecules. A design strategy for the rotation in a salt is discussed, based on the volume that the supramolecular cations occupy in the unit cell.     

Metal Complexes of Dithiolate Ligands: 5,6-Dihydro-1,4-dithiin-2,3-dithiolato (dddt(2-)), 5,7-Dihydro-1,4,6-trithiin-2,3-dithiolato (dtdt(2-)), and 2-Thioxo-1,3-dithiole-4,5-dithiolato (dmit(2-)). Synthesis, Electrochemical Studies, Crystal and Electronic Structures, and Conducting Properties

New precursors to potentially conductive noninteger oxidation state (NIOS) compounds based on metal complexes [ML(2)](n)()(-) [M = Ni, Pd, Pt; L = 5,6-dihydro-1,4-dithiin-2,3-dithiolato (dddt(2)(-)), 5,7-dihydro-1,4,6-trithiin-2,3-dithiolato (dtdt(2)(-)), and 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit(2)(-)); n = 2, 1, 0] have been investigated. Complexes of the series (NR(4))[ML(2)] (R = Me, Et, Bu; L = dddt(2)(-), dtdt(2)(-)) have been isolated and characterized, and the crystal structure of (NBu(4))[Pt(dtdt)(2)] (1) has been determined {1 = C(24)H(44)NPtS(10), a = 12.064(2) ?, b = 17.201(3) ?, c = 16.878(2) ?, beta = 102.22(2) degrees, V = 3423(1) ?(3), monoclinic, P2(1)/n, Z = 4}. Oxidation of these complexes affords the corresponding neutral species [ML(2)](0). Another series of general formula (cation)(n)()[M(dmit)(2)] [cation = PPN(+), BTP(+), and (SMe(y)()Et(3)(-)(y)())(+) with y = 0, 1, 2, and 3, n = 2, 1, M = Ni, Pd] has also been studied. All of these (cation)(n)()[M(dmit)(2)] complexes have been isolated and characterized [with the exception of (cation)[Pd(dmit)(2)] for cation = (SMe(y)()Et(3)(-)(y)())(+)]. The crystal structures of (PPN)[Ni(dmit)(2)].(CH(3))(2)CO (2) and (SMeEt(2))[Ni(dmit)(2)] (3) have been determined {2 = C(45)H(36)NNiS(10)P(2)O, a = 12.310(2) ?, b = 13.328(3) ?, c = 15.850(3) ?, alpha = 108.19(3) degrees, beta = 96.64(2) degrees, gamma = 99.67(2) degrees, V = 2373(1) ?(3), triclinic, P&onemacr;, Z = 2; 3 = C(11)H(13)NiS(11), a = 7.171(9) ?, b = 17.802(3) ?, c = 16.251(3) ?, beta = 94.39(4) degrees, V = 2068(2) ?(3), monoclinic, P2(1)/n, Z = 4} NIOS salts derived from the preceding precursors were obtained by electrochemical oxidation. Electrochemical studies of the [M(dddt)(2)] complexes show that they may be used for the preparation of NIOS radical cation salts and [M(dddt)(2)][M'(dmit)(2)](x)() compounds, but not for the preparation of (cation)[M(dddt)(2)](z)() NIOS radical anion salts. The electrochemical oxidation of the [M(dtdt)(2)](-) complexes always yields the neutral [M(dtdt)(2)](0) species. The crystal structure of [Pt(dddt)(2)][Ni(dmit)(2)](2) (4) has been determined and is consistent with the low compaction powder conductivity (5 x 10(-)(5) S cm(-)(1) at room temperature) {4 = C(20)H(8)Ni(2)PtS(28), a = 20.336(4) ?, b = 7.189(2) ?, c = 14.181(2) ?, beta = 97.16(2) degrees, V = 2057(1) ?(3), monoclinic, C2/m, Z = 2}. The crystal structures of the semiconducting NIOS compounds (BTP)[Ni(dmit)(2)](3) (5) and (SMe(3))[Ni(dmit)(2)](2) (6) have been determined {5 = C(43)H(22)PNi(3)S(30), a = 11.927(2) ?, b = 24.919(2) ?, c = 11.829(3) ?, alpha = 93.11(1) degrees, beta = 110.22(1) degrees, gamma = 83.94(1) degrees, V = 3284(1) ?(3), triclinic, P&onemacr;, Z = 2; 6 = C(15)H(9)Ni(2)S(21), a = 7.882(1) ?, b = 11.603(2) ?, c = 17.731(2) ?, alpha = 77.44(1) degrees, beta = 94.39(1) degrees, gamma = 81.27(1) degrees, V = 1563(1) ?(3), triclinic, P&onemacr;, Z = 2}. The parent compound (SEt(3))[Ni(dmit)(2)](z) (unknown stoichiometry) is also a semiconductor with a single-crystal conductivity at room temperature of 10 S cm(-)(1). By contrast, the single-crystal conductivity at room temperature of (SMeEt(2))[Pd(dmit)(2)](2) (7) is rather high (100 S cm(-)(1)). 7 behaves as a pseudometal down to 150 K and undergoes an irreversible metal-insulator transition below this temperature. The crystal structure of 7 has been determined {7 = C(17)H(13)NPd(2)S(21), a = 7.804(4) ?, b = 36.171(18) ?, c = 6.284(2) ?, alpha = 91.68(4) degrees, beta = 112.08(4) degrees, gamma = 88.79(5) degrees, V = 1643(1) ?(3), triclinic, P&onemacr;, Z = 2}. The electronic structure of (SMeEt(2))[Pd(dmit)(2)](2) (7) and the possible origin of the metal-insulator transition at 150 K are discussed on the basis of tight-binding band structure calculations.     

M+(12-crown-4) supramolecular cations (M+ = Na+, K+, Rb+, and NH4+) within Ni(2-thioxo-1,3-dithiole-4,5-dithiolate)2 molecular conductor

Monovalent cations (M+ = Na+, K+, Rb+, and NH4+) and 12-crown-4 were assembled to new supramolecular cation (SC+) structures of the M+(12-crown-4)n (n = 1 and 2), which were incorporated into the electrically conducting Ni(dmit)2 salts (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate). The Na+, K+, and Rb+ salts are isostructural with a stoichiometry of the M+(12-crown-4)2[Ni(dmit)2]4, while the NH4+ salt has a stoichiometry of NH4+(12-crown-4)[Ni(dmit)2]3(CH3CN)2. The electrical conductivities of the Na+, K+, Rb+, and NH4+ salts at room temperature are 7.87, 4.46, 0.78, and 0.14 S cm-1, respectively, with a semiconducting temperature dependence. The SC+ structures of the Na+, K+, and Rb+ salts have an ion-capturing sandwich-type cavity of M+(12-crown-4)2, in which the M+ ion is coordinated by eight oxygen atoms of the two 12-crown-4 molecules. On the other hand, the NH4+ ion is coordinated by four oxygen atoms of the 12-crown-4 molecule. Judging from the M(+)-O distances, thermal parameters of oxygen atoms, and vibration spectra, the thermal fluctuation of the Na+(12-crown-4)2 structure is larger than those of K+(12-crown-4)2 and Rb+(12-crown-4)2. The SC+ unit with the larger alkali metal cation gave a stress to the Ni(dmit)2 column, and the SC+ structure changed the pi-pi overlap mode and electrically conducting behavior.     

Magnetic semiconductor: structural,magnetic, and conducting properties of the salts of the 6-oxoverdazyl radical cation with M(dmit)(2) anions (M = Ni,Zn, Pd,and Pt,dmit = 1,3-dithiol-2-thione-4,5-dithiolate)

Five kinds of (1:1), (1:3), and (2:1) salts of 3-[4-(diethylmethylammonio)phenyl]-1,5-diphenyl-6-oxoverdazyl radical cation [V](+) with M(dmit)(2) anions (M = Ni, Zn, Pd, and Pt, dmit = 1,3-dithiol-2-thione-4,5-dithiolate) ([V](+)[Ni(dmit)(2)](-) (1), [V](+)[Ni(dmit)(2)](3)(-) (2), [V](+)(2)[Zn(dmit)(2)](2-) (3), [V](+)(2)[Pd(dmit)(2)](2-) (4), and [V](+)(2)[Pt(dmit)(2)](2-) (5)) and an iodide salt of [V](+) ([V](+)[I](-) (6)) have been prepared, and the magnetic susceptibilities (chi(M) values) have been measured between 1.8 and 300 K. The chi(M) of the (1:1) Ni salt (1) can be well reproduced by the sum of the contributions from (i) a Curie-Weiss system with a Curie constant (C) of 0.376 K emu/mol and a negative Weiss constant (theta) of -1.5 K and (ii) the one-dimensional Heisenberg antiferromagnetic alternating chain system with 2J(A-B)/k(B) = -274 K (alternation parameter alpha = J(A-C)/J(A-B) = 0.2). The chi(M) of the (1:3) Ni salt (2) can be well explained by the two-term contributions from (i) the Curie-Weiss system with C = 0.376 K emu/mol and theta = -5.0 K and (ii) the dimer system with 2J/k(B) = -258 K. The magnetic properties of 1 and 2 were discussed based on the results obtained by crystal structure analysis and ESR measurements of 1 and 2. The chi(M) values of the (2:1) Zn, Pd, Pt salts 3, 4, and 5 and [V](+)[I](-) salt 6 follow the Curie-Weiss law with C = 0.723, 0.713, 0.712, and 0.342 K emu/mol and theta = -2.8, -3.1, -2.6, and +0.02 K, respectively, indicating that only the spins of the verdazyl radical cation contribute to the magnetic property of these salts. The salts 1, 3, and 5 are insulators. On the other hand, the conductivity (sigma) of the Ni salt 2 and Pd salt 4 at 20 degrees C was sigma = 8.9 x 10(-2) and 1.3 x 10(-4) S cm(-)(1) with an activation energy E(A) = 0.11 and 0.40 eV, respectively. The salts 2 and 4 are new molecular magnetic semiconductors.     

Synthesis and characterization of the silver maleonitrilediselenolates and silver maleonitriledithiolates [K([2.2.2]-cryptand)]4[Ag4(Se2C2(CN)2)4], [Na([2.2.2]-cryptand)]4[Ag4(S2C2(CN)2)4].0.33MeCN, [NBu4]4[Ag4(S2C2(CN)2)4], [K([2.2.2]-cryptand)]3[Ag(Se2C2(CN)2)2].2MeCN, and [Na([2.2.2]-cryptand)]3[Ag(S2C2(CN)2)2

Reaction of AgBF(4), KNH(2), K(2)Se, Se, and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](4)[Ag(4)(Se(2)C(2)(CN)(2))(4)] (1). In the unit cell of 1 there are four [K([2.2.2]-cryptand)](+) units and a tetrahedral Ag(4) anionic core coordinated in mu(1)-Se, mu(2)-Se fashion by each of four mns ligands (mns = maleonitrilediselenolate, [Se(2)C(2)(CN)(2)](2)(-)). Reaction of AgNO(3), Na(2)(mnt) (mnt = maleonitriledithiolate, [S(2)C(2)(CN)(2)](2)(-)), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](4)[Ag(4)(mnt)(4)].0.33MeCN (2). The Ag(4) anion of 2 is analogous to that in 1. Reaction of AgNO(3), Na(2)(mnt), and [NBu(4)]Br in acetonitrile yields [NBu(4)](4)[Ag(4)(mnt)(4)] (3). The anion of 3 also comprises an Ag(4) core coordinated by four mnt ligands, but the Ag(4) core is diamond-shaped rather than tetrahedral. Reaction of [K([2.2.2]-cryptand)](3)[Ag(mns)(Se(6))] with KNH(2) and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](3)[Ag(mns)(2)].2MeCN (4). The anion of 4 comprises an Ag center coordinated by two mns ligands in a tetrahedral arrangement. Reaction of AgNO(3), 2 equiv of Na(2)(mnt), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](3)[Ag(mnt)(2)] (5). The anion of 5 is analogous to that of 4. Electronic absorption and infrared spectra of each complex show behavior characteristic of metal-maleonitriledichalcogenates. Crystal data (153 K): 1, P2/n, Z = 2, a = 18.362(2) A, b = 16.500(1) A, c = 19.673(2) A, beta = 94.67(1) degrees, V = 5941(1) A(3); 2, P4, Z = 4, a= 27.039(4) A, c = 15.358(3) A, V = 11229(3) A(3); 3, P2(1)/c, Z = 6, a = 15.689(3) A, b = 51.924(11) A, c = 17.393(4) A, beta = 93.51(1) degrees, V = 14142(5) A(3); 4, P2(1)/c, Z = 4, a = 13.997(1) A, b = 21.866(2) A, c = 28.281(2) A, beta = 97.72(1) degrees, V = 8578(1) A(3); 5, P2/n, Z = 2, a = 11.547(2) A, b = 11.766(2) A, c = 27.774(6) A, beta = 91.85(3) degrees, V = 3772(1) A(3).     

Dodecahydroxy-closo-dodecaborate(2-).

The cesium salt of the icosahedral borane anion dodecahydroxy-closo-dodecaborate(2-), Cs(2)[closo-B(12)(OH)(12)], Cs(2)1, was prepared by heating cesium dodecahydro-closo-dodecaborate(2-), Cs(2)[closo-B(12)H(12)], Cs(2)2, with 30% hydrogen peroxide. The other alkali metal salts A(2)1 (A = Li, Na, K, Rb) precipitated upon addition of ACl to warm aqueous solutions of Cs(2)1. The ammonium salt, [NH(4)](2)1, and the (mu-nitrido)bis(triphenylphosphonium) salt, [PPN](2)1, were obtained similarly. The [H(3)O](2)1 salt precipitated upon acidification of aqueous solutions of Cs(2)1 with hydrochloric acid. The solubility of these salts in water was determined by measuring the boron content of saturated aqueous solutions of A(2)1 (A = Li, Na, K, Rb, Cs), [H(3)O](2)1, and [NH(4)](2)1 using ICP-AES. Although these salts are derived from a dianion with twelve pendant hydroxyl groups, the alkali metal salts surprisingly displayed low water solubilities. Water solubility decreases with a decrease in the radius of A(+), except for the lithium salt, which is slightly more soluble than the potassium salt. The [H(3)O](2)1 and the [NH(4)](2)1 salts provide rare examples of water-insoluble hydronium and ammonium salts. The low water solubility of the A(2)1 salts is attributed to the dianion's pendant hydroxyl groups, which appear to function as cross-linking ligands. Four alkali metal salts, A(2)1 (A = Na, K, Rb, Cs), were characterized in the solid state by single-crystal X-ray crystallography. These data revealed intricate networks in which several anions are complexed through their hydroxyl groups to each alkali metal cation. In addition, the anions are engaged in hydrogen bonding with each other and, if present, with water of hydration. This cross-linking results in the precipitation of aggregated salts. Cation coordination numbers decrease with cation radius. Thus, cesium and rubidium are ten-coordinate, whereas potassium is seven-coordinate and sodium is six-coordinate. The geometry of anion 1(2)(-) is independent of cation identity; the B-B and B-O bond lengths of the various A(2)1 salts (A = Na, K, Rb, Cs) are identical.     

Molecular paramagnetic semiconductor: crystal structures and magnetic and conducting properties of the Ni(dmit)(2) salts of 6-oxoverdazyl radical cations (dmit = 1,3-dithiol-2-thione-4,5-dithiolate)

Four kinds of 1:1 and 1:3 salts of 3-[4-(trimethylammonio)phenyl]-1,5-diphenyl-6-oxoverdazyl radical cation ([1](+)) and its mono- and dimethyl derivatives ([2](+) and [3](+)) with Ni(dmit)(2) anions (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) ([1](+)[Ni(dmit)(2)](-) (4), [2](+)[Ni(dmit)(2)](-) (5), [3](+)[Ni(dmit)(2)](-) (6), and [1](+)[Ni(dmit)(2)](3)(-) (7)) have been prepared, and the magnetic susceptibilities (chi(M)) have been measured between 1.8 and 300 K. The chi(M) values of salts 5 and 7 can be well reproduced by the sum of the contributions from (i). a Curie-Weiss system with a Curie constant of 0.376 (K emu)/mol and negative Weiss constants (THETAV;) of -0.4 and -1.7 K and (ii). a dimer system with strong negative exchange interactions of 2J/k(B) = -354 and -258 K, respectively. The dimer formations in Ni(dmit)(2) anions have been ascertained by the crystal structure analyses of salts 4-6. In salts 4 and 6, Ni(dmit)(2) dimer molecules are sandwiched between two verdazyl cations, indicating the formation of a linear tetramer in 4 and 6. The magnetic susceptibility data for salts 4 and 6 have been fitted to a linear tetramer model using an end exchange interaction of 2J(1)/k(B) = -600 K and a central interaction of 2J(2)/k(B) = -280 K for 4 and 2J(1)/k(B) = -30 K and 2J(2)/k(B) = -580 K for 6, respectively. The results of the temperature dependence of the g(T) value in salts 4-6 obtained by ESR measurement also support the above analyses. The 1:1 salts 4-6 are insulators. On the other hand, the conductivity of the 1:3 salt 7 at 20 degrees C was sigma = 0.10 S cm(-)(1) with an activation energy E(A) = 0.099 eV, showing the semiconductor property. Salt 7 is a new molecular paramagnetic semiconductor.     

New metalloligands [M(SC[O]Ph)(4)](-): synthesis and characterization of polymeric [A(MeCN)(x)[M(SC[O]Ph)(4)]] compounds (A = Li,Na and K; M = Ga and In; x = 0-2)

Exploiting the ability of the [M(SC[O]Ph)(4)](-) anion to behave like an anionic metalloligand, we have synthesized [Li[Ga(SC[O]Ph)(4)]] (1), [Li[In(SC[O]Ph)(4)]] (2), [Na[Ga(SC[O]Ph)(4)]] (3), [Na(MeCN)[In(SC[O]Ph)(4)]] (4), [K[Ga(SC[O]Ph)(4)]] (5), and [K(MeCN)(2)[In(SC[O]Ph)(4)]] (6) by reacting MX(3) and PhC[O]S(-)A(+) (M = Ga(III) and In(III); X = Cl(-) and NO(3)(-); and A = Li(I), Na(I), and K(I)) in the molar ratio 1:4. The structures of 2, 4, and 6 determined by X-ray crystallography indicate that they have a one-dimensional coordination polymeric structure, and structural variations may be attributed to the change in the alkali metal ion from Li(I) to Na(I) to K(I). Crystal data for 2 x 0.5MeCN x 0.25H(2)O: monoclinic space group C2/c, a = 24.5766(8) A, b = 13.2758(5) A, c = 19.9983(8) A, beta = 108.426(1) degrees, Z = 8, and V = 6190.4(4) A(3). Crystal data for 4: monoclinic space group P2(1)/c, a = 10.5774(7) A, b = 21.9723(15) A, c = 14.4196(10) A, beta = 110.121(1) degrees, Z = 4, and V = 3146.7(4) A(3). Crystal data for 6: monoclinic space group P2(1)/c, a = 12.307(3) A, b = 13.672(3) A, c = 20.575(4) A, beta = 92.356(4) degrees, Z = 4, and V = 3458.8(12) A(3). The thermal decomposition of these compounds indicated the formation of the corresponding AMS(2) materials.     

Between Ni(mnt)2 and Ni(tfd)2 dithiolene complexes: the unsymmetrical 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate and its nickel complexes

A novel 1,2-dithiolate ligand, that is, the 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate, abbreviated here as tfadt, is prepared from the corresponding cyclic dithiocarbonate. This ligand, substituted with both a CN and a CF(3) group, is compared with the well-known maleonitrile- and bis(trifluoromethyl)ethane-1,2-dithiolates. The preparation, electrochemical properties, and X-ray crystal structures of the square-planar nickel complexes, in both their dianionic diamagnetic [Ni(tfadt)(2)](2)(-) and their monoanionic paramagnetic [Ni(tfadt)(2)](*)(-) forms, are reported, as n-Bu(4)N(+), PPh(4)(+), and (18-crown-6)Na(+) salts, respectively. In the [(18-crown-6)Na](2)[Ni(tfadt)(2)] salt, each CN moiety of the [Ni(tfadt)(2)](2)(-) dianion is coordinated to a (18-crown-6)Na(+) cation through a CN...Na interaction [N...Na = 2.481(3) A], affording an "axle with wheels" model where two MeOH molecules act as axle caps. On the other hand, in [(18-crown-6)Na][Ni(tfadt)(2)], each (18-crown-6)Na(+) cation is coordinated on both sides by the CN groups of two monoanionic [Ni(tfadt)(2)](*)(-) complexes with N...Na(+) distances at 2.434(5) and 2.485(4) A, giving rise to heterobimetallic chains with alternating (18-crown-6)Na(+) and [Ni(tfadt)(2)](*)(-) ions. These two examples demonstrate the attractive ability of the CN moieties in the [Ni(tfadt)(2)](2)(-)(,)(*)(-) complexes to coordinate metallic cationic centers. The paramagnetic salts of the anionic [Ni(tfadt)(2)](*)(-) complex follow Curie-type law in the 2-300 K temperature range, indicating the absence of intermolecular magnetic interactions in the solid state. The complexes are found in their trans form in all crystal structures, while density functional theory calculations establish that both forms have essentially the same energy. A cis-trans interconversion process is observed by variable-temperature NMR on the dianionic [Ni(tfadt)(2)](2)(-) complex with a coalescence temperature T(c) of 260 K and a free energy of activation of 51-53 kJ mol(-)(1).     

Towards Single-component Molecular Conductor [Ni(dmit)_2] by Charge Disproportionation:2[Ni(dmit)_2]~(-0.5)[Ni(dmit)_2]+[Ni(dmit)_2]~-

It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…     

Solid-state molecular rotators of anilinium and adamantylammonium in [Ni(dmit)2](-) salts with diverse magnetic properties

Supramolecular rotators of hydrogen-bonding assemblies between anilinium (Ph-NH 3 (+)) or adamantylammonium (AD-NH 3 (+)) and dibenzo[18]crown-6 (DB[18]crown-6) or meso-dicyclohexano[18]crown-6 (DCH[18]crown-6) were introduced into [Ni(dmit) 2] salts (dmit (2-) is 2-thioxo-1,3-dithiole-4,5-dithiolate). The ammonium moieties of Ph-NH 3 (+) and AD-NH 3 (+) cations were interacted through N-H (+) approximately O hydrogen bonding with the six oxygen atoms of crown ethers, forming 1:1 supramolecular rotator-stator structures. X-ray crystal-structure analyses revealed a jackknife-shaped conformation of DB[18]crown-6, in which two benzene rings were twisted along the same direction, in (Ph-NH 3 (+))(DB[18]crown-6)[Ni(dmit) 2] (-) ( 1) and (AD-NH 3 (+))(DB[18]crown-6)[Ni(dmit) 2] (-) ( 3), whereas the conformational flexibility of two dicyclohexyl rings was observed in (Ph-NH 3 (+))(DCH[18]crown-6)[Ni(dmit) 2] (-) ( 2) and (AD-NH 3 (+))(DCH[18]crown-6)[Ni(dmit) 2] (-) ( 4). Sufficient space for the molecular rotation of the adamantyl group was achieved in the crystals of salts 3 and 4, whereas the rotation of the phenyl group in salts 1 and 2 was rather restricted by the nearest neighboring molecules. The rotation of the adamantyl group in salts 3 and 4 was evidenced from the temperature-dependent wide-line (1)H NMR spectra, dielectric properties, and X-ray crystal structure analysis. ab initio calculations showed that the potential energy barriers for the rotations of adamantyl groups in salts 3 (Delta E approximately 18 kJmol (-1)) and 4 (Delta E approximately 15 kJmol (-1)) were similar to those of ethane ( approximately 12 kJmol (-1)) and butane (17-25 kJmol (-1)) around the C-C single bond, which were 1 order of magnitude smaller than those of phenyl groups in salts 1 (Delta E approximately 180 kJmol (-1)) and 2 (Delta E approximately 340 kJmol (-1)). 1D or 2D [Ni(dmit) 2] (-) anion arrangements were observed in the crystals according to the shape of crown ether derivatives. The 2D weak intermolecular interactions between [Ni(dmit) 2] (-) anions in salts 1 and 3 led to Curie-Weiss behavior with weak antiferromagnetic interaction, whereas 1D interactions through lateral sulfur-sulfur atomic contacts between [Ni(dmit) 2] (-) anions were observed in salts 2 and 4, whose magnetic behaviors were dictated by ferromagnetic (salt 2) and singlet-triplet (salt 4) intermolecular magnetic interactions, respectively.     

Towards Single-component Molecular Conductor [Ni（dmit）2 ] by Charge Disproportionation： 2[Ni（dmit）2]^0.5→[Ni（dmit）2 ]＋ [Ni（dmit）2]^-

A new method of synthesizing single-component molecular conductor [Ni(dmit)2] bythe reaction 2(Me4N)[Ni(dmit)2]2→ [Ni(dmit)2] (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2]exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.     

Novel aggregation of [Ni(thiolato)2(amine)2]-type square planes assisted by silver(I) ions

Treatment of [Ni(L)][L =((-)SCH(2)CH(2)NH[double bond, length as m-dash]C(CH(3))-)(2)] with Ag(+) in water gave a pinwheel-like S-bridged Ni(II)(3)Ag(I)(2) structure in [Ag(2)[Ni(L)](3)](2+), which further reacted with [Ni(L)] to produce a Ni(II)(4)Ag(I)(2) structure in [Ag(2)[Ni(L)](4)](2+) and a Ni(II)(7)Ag(I)(4) structure in [Ag(4)[Ni(L)](7)](4+).     

Supramolecular rotor: adamantylammonium([18]crown-6) in [Ni(dmit)2]- salt

Adamantylammonium (ADNH3+) was complexed with [18]crown-6, forming a supramolecular cation of (ADNH3+)([18]crown6), which was introduced into a [Ni(dmit)2]- salt as a supramolecular rotor. The cation layers were alternately arranged with [Ni(dmit)2]- layers in the crystal, in which the molecular rotation of (ADNH3+)([18]crown-6) was confirmed from the temperature-dependent solid-state 1H NMR.     

Molecular rotor of Cs2([18]crown-6)3 in the solid state coupled with the magnetism of [Ni(dmit)2

Nanoscale molecular rotors that can be driven in the solid state have been realized in Cs2([18]crown-6)3[Ni(dmit)2]2 crystals. To provide interactions between the molecular motion of the rotor and the electronic system, [Ni(dmit)2]- ions, which bear one S=1/2 spin on each molecule, were introduced into the crystal. Rotation of the [18]crown-6 molecules within a Cs2([18]crown-6)3 supramolecule above 220 K was confirmed using X-ray diffraction, NMR, and specific heat measurements. Strong correlations were observed between the magnetic behavior of the [Ni(dmit)2]- ions and molecular rotation. Furthermore, braking of the molecular rotation within the crystal was achieved by the application of hydrostatic pressure.     

(Bu_4N)[Ni(dmit)_2]的一步合成及一种新晶相

用中心离子替代和空气自动氧化的方法由(Bu_4N)_2[Zn(dmit)_2]一步合成了 (Bu_4N)[Ni(dmit)_2]，这种方法可推广到其它Z[M(dmit)_2]配合物和Z[M(dmit) _2]_2导电配合物的合成(Bu_4N)[Ni(dmit)_2]结晶过程中出现两个晶相，其中空间 群为C2/c的侧心单斜相为新晶相，X射线结构测定结果为：a=2.0191(2)nm, b=1. 3404(1) nm,β=105.55(1)~°,V=3165.5(6)nm~3, R=0.055,　晶体中的Ni(dmit) _2]－呈D_(2h)点群对称性，平面性接近完美，共轭性相当显著，相邻Ni(dmit)_2] －平面间的夹角为75.56（3）~°。     

Cationic assembly of metal complex aggregates: structural diversity,solution stability,and magnetic properties

The tetradentate imino-carboxylate ligand [L](2)(-) chelates the equatorial sites of Ni(II) to give the complex [Ni(L)(MeOH)(2)] in which a Ni(II) center is bound in an octahedral coordination environment with MeOH ligands occupying the axial sites. Lanthanide (Ln) and Group II metal ions (M) template the aggregation of six [Ni(L)] fragments into the octahedral cage aggregates (M[Ni(L)](6))(x)(+) (1: M = Sr(II); x = 2,2: M = Ba(II); x = 2, 3: M = La(III); x = 3, 4: M = Ce(III); x = 3, 5: M = Pr(III); x = 3, and 6: M = Nd(III); x = 3). In the presence of Group I cations, however, aggregates composed of the alkali metal-oxide cations template various cage compounds. Thus, Na(+) forms the trigonal bipyramidal [Na(5)O](3+) core within a tricapped trigonal prismatic [Ni(L)](9) aggregate to give ((Na(5)O) subset [Ni(L)](9)(MeOH)(3))(BF(4))(2).OH.CH(3)OH, 7. Li(+) and Na(+) together form a mixed Li(+)/Na(+) core comprising distorted trigonal bipyramidal [Na(3)Li(2)O](3+) within an approximately anti-square prismatic [Ni(L)](8) cage in ((Na(3)Li(2)O) subset [Ni(L)](8)(CH(3)OH)(1.3)(BF(4))(0.7))(BF(4))(2.3).(CH(3)OH)(2.75).(C(4)H(10)O)(0.5), 8, while in the presence of Li(+), a tetrahedral [Li(4)O](2+) core within a hexanuclear open cage [Ni(L)](6) in ((Li(4)O) subset [Ni(L)](6)(CH(3)OH)(3))2ClO(4).1.85CH(3)OH, 9, is produced. In the presence of H(2)O, the Cs(+) cation induces the aggregation of the [Ni(L)(H(2)O)(2)] monomer to give the cluster Cs(2)[Ni(L)(H(2)O)(2)](6).2I.4CH(3)OH.5.25H(2)O, 10. Analysis by electronic spectroscopy and mass spectrometry indicates that in solution the trend in stability follows the order 1-6 > 7 > 8 approximately 9. Magnetic susceptibility data indicate that there is net antiferromagnetic exchange between magnetic centers within the cages.