Structural diversity among copper(I) ethylene adducts of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine.

The reaction of Cu(ClO(4))·6H(2)O, Cu turnings, and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) in Me(2)CO under C(2)H(4) afforded brownish-red needle crystals of {[Cu(2)(bptz˙(-))(C(2)H(4))(2)](ClO(4))}(2) (1) as a minor product and brown plate crystals of [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](ClO(4))(2)·2Me(2)CO (2). The X-ray crystallographic study showed that complex 1 is composed of two independent [Cu(2)(bptz˙(-))(C(2)H(4))(2)](+) cation moieties and two ClO(4)(-) anions. In both of the cation moieties, each Cu(I) atom is coordinated by two chelate N atoms of bptz˙(-) and the C=C bond of C(2)H(4) in the trigonal-planar geometry to form a unique transoid dinuclear Cu(I)-bptz˙(-)/C(2)H(4) adduct bearing a metal-stabilized tetrazine anion radical, bptz˙(-), which was produced by the one-electron reduction of bptz. In contrast, complex 2 consists of one [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moiety, two ClO(4)(-) anions, and two solvated Me(2)CO molecules. Each Cu(I) atom is coordinated by two chelate N atoms of 2,5-H(2)bptz and the C=C bond of C(2)H(4) in the trigonal-planar geometry to afford a transoid dinuclear Cu(I)-C(2)H(4) adduct with 2,5-H(2)bptz, which was produced by the two-electron reduction of bptz. Additionally, the similar reaction of Cu(ClO(4))·6H(2)O, Cu turnings, and bptz in Me(2)CO or MeEtCO under C(2)H(4) in the presence of ferrocene afforded orange brick crystals of [Cu(2)(bpdpyz)(C(2)H(4))(2)](ClO(4))(2)·Me(2)CO (3) and [Cu(2)(bpdpyz)(C(2)H(4))(2)](ClO(4))(2) (4), respectively, together with complex 1 in higher yield. This result shows that 3,6-bis(2-pyridyl)-4,5-dihydropyridazine (bpdpyz) was produced by the cycloaddition of bptz with C(2)H(4)via a Diels-Alder addition and retro-Diels-Alder elimination of dinitrogen. In complexes 3 and 4, each Cu(I) atom is coordinated by two chelate N atoms of bpdpyz and the C=C bond of C(2)H(4) to afford an unusual cisoid dinuclear Cu(I)-C(2)H(4) adduct. Further attempts to react excess [Cu(C(2)H(4))(n)]ClO(4) with bptz in Me(2)CO under C(2)H(4) afforded black brick crystals of [Cu(4)(4,5-H(2)bptz)(4)](ClO(4))(4)·2Me(2)CO (5) together with complex 1. Complex is the first [4 × 4] grid-like tetranuclear Cu(I) complex constructed by the combination of Cu(I) ion and 4,5-H(2)bptz. The four Cu(I) atoms are spanned by four 4,5-H(2)bptz ligands, with two lying above the Cu(4) mean plane and two lying below. In contrast, the similar reaction of excess [Cu(C(2)H(4))(n)]ClO(4) with bptz in Me(2)CO under C(2)H(4) in the presence of ferrocene afforded reddish-brown brick crystals of {[Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](ClO(4))(2)}(2)·Me(2)CO (6) together with complexes 1 and 5. Complex 6 is composed of two independent [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moieties, four ClO(4)(-) anions, and a solvated Me(2)CO molecule. It is interesting that the structures of the two [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moieties are different: one has a nearly planar structure and the other possesses a boat conformation owing to the bent central dihydrotetrazine ring.

A unique chair-shaped hexanuclear Cu(I) metallamacrocyclic C2H4 adduct encapsulating a BF4- anion.

Three novel Cu(I)-C2H4 adducts bearing 4-(2-pyridyl)pyrimidine were self-assembled, and the roles of anion and solvent were proved in the formation process.

{6,6'-Dimeth-oxy-2,2'-[o-phenyl-enebis(nitrilo-methyl-idyne)]diphenolato}cobalt(II) dichloro-methane disolvate.

The title compound, [Co(C(22)H(18)N(2)O(4))]·2CH(2)Cl(2), was isolated from the reaction of N,N'(o-phenyl-ene)bis-(vanillalimine) (H(2)L) with Co(SCN)(2). The crystal structure contains a Co(II) ion surrounded by the L(2-) ligand in a slightly distorted square-planar fashion. Inter-molecular C-H⋯O hydrogen-bonding contacts between the dichloro-methane solvent mol-ecules and the meth-oxy or carboxyl-ate O atoms are observed in the crystal structure. The planar complex mol-ecules stack through inversion related π-π inter-actions between the six-membered rings of the vanillalimine half ligands. The distance between centroids is 3.498 (2) Šand the perpendicular distance is 3.345 Å. A partial stacking is observed with a centroid-centroid distance of 3.830 (2) Å, a perpendicular distance of 3.350 Šand a slippage of 1.856 Å.

Bowl-shaped Cu(I) metallamacrocyclic ethylene and carbonyl adducts as structural analogues of organic calixarenes.

Three novel Cu(I) metallacalixarenes with C(2)H(4) and CO legs, in which an anion is accommodated in the inside cavity, were self-assembled by anion templation and have been structurally characterized.

Photochromism of novel metal coordination polymers with 1,2-Bis(2'-methyl-5'-(carboxylic acid)-3'-thienyl)perfluorocyclopentene in the crystalline phase.

Three new metal complexes with 1,2-bis(2'-methyl-5'-(carboxylic acid)-3'-thienyl)perfluorocyclopentene (BM-5-CATP) were synthesized and characterized by X-ray diffraction analysis. BM-5-CATP serves as a bis-monodentate ligand that bridges metal centers to generate three 1D polymers. The two thienyl rings in the three complexes adopt antiparallel fashions, and the distances of 3.39, 3.53, and 3.57 A between the two reactive carbons are short enough to allow photocyclizations to occur in the crystalline phase. [Co(BM-5-CATP)(py)2(MeOH)2] (1) displayed effective photoisomerization in the crystalline phase. Interestingly, solvated 1 underwent a solid-state conversion upon heating to generate, through the release of the coordinated MeOH and rearrangement of the coordination geometry, the desolvated form (1a), while maintaining reversible photochromism. The removal of the solvent led to obvious changes in physical properties such as color and magnetic properties. The ESR spectra of 1 and 1a changed reversibly upon photoexcitation, indicating changes in coordination geometry accompanied by photoreaction. The magnetic susceptibilities of 1 and 1a showed no obvious changes, suggesting that the cobalt-cobalt interaction through the long bridging BM-5-CATP is less effective. Both [Cu(BM-5-CATP)(py)3](EtOH)(py)1.8 (2) and [Zn(BM-5-CATP)(phen)(H2O)] (3) exhibited reversible photoreactions in the crystalline phase. However, 3 did not show remarkable spectral changes because of steric hindrance from the coordinated bulky phenanthroline and the intramolecular H bonds.

Sandwich-shaped silver(I) metallomacrocycles encapsulating a XF6(2-) (X = Si, Ge and Sn) anion.

A series of sandwich-shaped complexes based on two square tetranuclear Ag(I) metallomacrocycles, [[Ag4(pprd)4]2(XF6)]-(BF4)6.8MeNO2 (pprd = 4-(2-pyridyl)pyrimidine; X = Si, Ge and Sn), in which a XF6(2-) anion is encapsulated, were prepared and their structures were characterized both in the solid state and solution.

(mu-2,11-Dithia[3.3]paracyclophane-kappa2S:S')bis[(6-carboxypyridine-2-carboxylato-kappa2N,O6silver(I)]: a mixed-ligand silver-based dinuclear compound.

In the title complex, [Ag2(C7H4NO4)2(C16H16S2)], each Ag(I) atom is trigonally coordinated by one S atom of a 2,11-dithia[3.3]paracyclophane (dtpcp) ligand, and by one N and one O atom of a 6-carboxypyridine-2-carboxylate ligand. Dtpcp acts as a bidentate ligand, bridging two inversion-related AgI atoms to give a dinuclear silver(I) compound. The dinuclear moieties are interconnected via O-H...O hydrogen bonds to form a two-dimensional zigzag sheet. Two such sheets are interwoven via pi-pi interactions between pyridine rings, affording an interwoven bilayer network.

Silver(I) coordination polymers of fluorescent oligo(phenylenevinylene) with pi-pi stackings: luminescence and conductivity.

Three luminescent silver(I)-oligo(phenylenevinylene) complexes, [Ag2(bmsb)(ClO4)2] (1), [Ag2(bmsb)(H2O)4](BF4)2 (2), and [Ag2(bdb)(CF3SO3)2] (3) (bmsb = 1, 4-bis(methylstyryl)benzene, bdb = 4,4'-bis(2, 5-dimethylstryryl)biphenyl), have been synthesized and structurally characterized. Complexes 1 and 2 are 2D networks with unique metallocyclophane motifs. Complex 3 affords a 2D zigzag sheet, in which silver triflates form tubelike double chains and bdb molecules act as linkages. Complex 2 exhibits high electric conductivity because of columnar aromatic stackings formed through intra- and intermolecular pi-pi interactions. Complexes 1-3 in the solid state exhibit luminescence, of which excitation and emission maxima are shifted to longer wavelength as compared to those of the corresponding metal-free ligands.

Silver(I) compounds consisting of [2.2]paracyclophane: reversible guest-driven solid-state transformation and incorporation behavior.

Reaction of [2.2]paracyclophane with silver(I) heptafluorobutyrate (AgC3F7CO2) has isolated three novel networks: [Ag4(pcp)(C3F7CO2)4] x pyrene (1), [Ag4(pcp)(C3F7CO2)4] x phen (phen = phenanthrene) (2), and [Ag4(pcp)(C3F7CO2)4] x fluorene (3), and an intercalation compound [Ag4(pcp)(C3F7CO2)4] x 2benzene (4). All the four complexes exhibit two-dimensional (2D) sheet structures in which AgC3F7CO2 form an infinite chain and pcp acts as linkage. 1, 2, and 3 show 2D flat sheets with cavities in which guest molecules are situated, whereas 4 exhibits 2D zigzag layers between which guest benzene molecules are intercalated. Pcp shows mu-di-eta1-eta2 coordination mode in 1, mu-tetra-eta1 coordination mode in 2 and 3, and mu-tetra-eta2 coordination mode in 4. The reversible guest exchanges were observed between complex 1, 2, or 3 and intercalation compound 4. It is unprecedented for metal-organic inclusion complexes that the guest exchange occurs where the guest is the solute molecule. Furthermore, 4 can release the guest, and the original framework was completely recovered after reincorporation of benzene. It should be noted that 4 can incorporate pyrene, phen, and fluorene to give 1, 2, and 3, respectively, after desorption.

catena-Poly[[chlorodipyridinemanganese(II)]-mu3-6-oxo-1,6-dihydropyridine-2-carboxylato].

The title one-dimensional chain polymer complex, [Mn(C6H4NO3)Cl(C6H5N)2]n, was isolated from the reaction of MnCl2 with 6-oxo-1,6-dihydropyridine-2-carboxylic acid (HpicOH) in pyridine. The asymmetric unit contains one [Mn(HPicO)Cl(py)2] moiety (py is pyridine), with the (HpicO)- ligand acting in a tridentate manner via the two carboxylate O atoms and the pyridone O atom. The operation of inversion centres generates eight- and 14-membered rings and, in conjunction with an a-axis translation, leads to an infinite chain extending along [100]. The Mn...Mn separations in this chain are 5.1069 (6) and 7.1869 (6) A. The MnII atom has a distorted octahedral coordination, with trans-axial pyridine ligands and with three O atoms and the Cl atom in the equatorial plane. The conformation of the 14-membered ring is stabilized by pairs of inversion-related N-H...O hydrogen bonds.

A Mn12 single-molecule magnet [Mn12O12(OAc)12(dpp)4] (dppH = diphenyl phosphate) with no coordinating water molecules.

The preparation and physical characterization are reported for a novel single-molecule magnet [Mn(12)O(12)(OAc)(12)(dpp)(4)] (dppH = diphenyl phosphate) with no coordinating water molecules. The crystal structure analysis reveals that there are four five-coordinate Mn(III) ions with Mn.H approaches. Addition of water in CD(2)Cl(2) solution was monitored by (1)H NMR, which showed that H(2)O could coordinate to a vacant site of a five-coordinate Mn(III) ion in solution. The measurements and analyses of magnetization hysteresis and ac magnetic susceptibility indicate that the title complex is a single-molecule magnet with a quantum tunneling behavior, whose ground state was tentatively assigned to S = 10 with g = 1.78 and D = -0.60 K.

Bis(mu-6-hydroxypicolinato)-mu-oxo-bis[dipyridinemanganese(III)] monohydrate.

The title compound, [Mn2(mu-O)(C6H3NO3)2(C5H5N)4].H2O, was isolated from the reaction of 2,6-pyridinedicarboxylic acid with [Mn12O12(CH3COO)16(H2O)4] in pyridine. The dimanganese complex has twofold symmetry; the MnIII atoms are bridged by one oxo and two amidate ligands and show compressed octahedral Jahn-Teller distortion. The molecular packing comprises a three-dimensional structure constructed by means of extensive intermolecular interactions, including three kinds of hydrogen bonds and pi-pi interactions.

Conversion of phenyl-substituted cyclopentadienes to pyrylium cations.

Phenyl-substituted cyclopentadienes are proved to form phenylated pyrylium cations in the presence of silver(I) perchlorate by insertion of an oxygen atom into the cyclopentadiene-ring. Three phenylated pyrylium compounds, [(Ph(5)C(5)O(+))(ClO(4)(-))](2)(CH(2)Cl(2)) (1), Ag(ClO(4))(H(2)O)(Ph(4)HC(5)O(+)) (ClO(4)(-)) (2), and (Ph(3)H(2)C(5)O(+))(ClO(4)(-)) (3) have been synthesized and characterized. A possible reaction pathway and formation mechanism of the pyrylium cation are proposed and discussed.

Syntheses, structures, and properties of intercalation compounds of silver(I) complex with [2.2]paracyclophane.

Reaction of [2.2]paracyclophane (pcp) with silver(I) trifluoroacetate (AgCF(3)CO(2)) and silver(I) pentafluoroproprionate (AgC(2)F(5)CO(2)) has led to isolation of three novel intercalation polymers: [Ag(4)(pcp)(CF(3)CO(2))(4)](C(6)H(6)) (1), [Ag(4)(pcp)(CF(3)CO(2))(4)](C(6)H(3)Me(3)) (2), and [Ag(4)(pcp)(C(2)F(5)CO(2))(4)](pcp) (3). Structure studies using single crystal X-ray diffraction have shown that all compounds contain two-dimensional layered frameworks based on cation-pi interactions, in which pcp exhibits an unprecedented micro-tetra-eta(2) coordination mode. Guest molecules which weakly interact with the host pcp via C-H.pi interactions are intercalated between layers. The guest-eliminated complexes (1a and 2a) and guest-reincorporated ones (1b or 1c and 2b or 2c), accompanied by small structural changes, were confirmed by (1)H NMR, thermogravimetric analysis, mass spectra, and X-ray powder diffraction patterns. The structural changes from 1 --> 1a --> 1c (=1) can take place reversibly in the process of exposure of 1a to benzene vapor. The original framework of complex 2 is also completely recovered by immersing 2a in mesitylene as well as exposing it to mesitylene vapor.

Construction of the multidecker anthracene-silver(I) system by intramolecular pi-pi interactions.

As a continuation of the study on the construction of the multidecker aromatic compounds with pi-pi interactions, the anthracene derivatives 9,10-dimethylanthracene (dman), 9,10-diphenylanthracene (dpan), and 7,12-dimethylbenz[a]anthracene (dmban) have been studied toward complexation with the silver(I) ion. The crystal structures of [Ag(dman)(0.5)(p-xylene)(ClO(4))], [Ag(2)(dpan)(0.5)(C(6)H(6))(0.5)(CF(3)SO(3))(2)], and [Ag(2)(dmban)(2)(ClO(4))(2)](p-xylene), together with the metal-free ligand dpan, have been determined by single-crystal X-ray diffraction. These pi-electron-rich aromatic compounds are found to have great promise as an approach to the effective self-assembly of high nuclearity in a multilayer fashion.

Syntheses and structures of photochromic silver(I) coordination polymers with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene.

Five novel silver(I) coordination polymers with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3- thienyl)ethene (cis-dbe) were synthesized and are characterized in this paper. Treatment of AgCF(3)SO(3) or AgCF(3)CO(2) with cis-dbe afforded [Ag(2)(cis-dbe)(CF(3)SO(3))(2)] (1) and [Ag(2)(cis-dbe)(CF(3)CO(2))(2)] (2), and both complexes exhibit a 1-D infinite chain structure with two cyano groups and two thienyl groups of the ligand bridging four metal ions. Reaction of AgC(n)()F(2)(n)(+1)CO(2) with cis-dbe gave rise to an unprecedented cocrystallization of a 2-D sheet structure, [Ag(2)(cis-dbe)(C(n)F(2)(n)(+1)CO(2))(2)], where n = 2 (3), 3 (4), and 4 (5). Upon irradiation with 450 nm light, these five silver(I) complexes turned orange or red from yellow, and the color reverted to yellow on exposure to 560 nm light, indicative of the reversible cyclization/ring-opening reaction occurring in the crystalline phase. Furthermore, different anions gave not only the different structural dimensions but also the different photoresponsive patterns. The correlation between the crystal structures and the photochromic reactivity is discussed.

Benzenthiolate bridged binuclear group 12 metal complexes with TTF fused dithiolate ligand, a new synthetic approach using cluster-cracking reaction.

Novel binuclear dithiolate complexes (Me4N)2[M2-(SPh)2(S2TTF(SMe)2)2] (M = Cd and Zn) have been synthesized by a new cluster-cracking method.

Construction of Copper(I) Coordination Polymers of 1,2,4,5-Tetracyanobenzene with Zigzag Sheet and Porous Frameworks.

This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies and properties. The reaction of [Cu(CH(3)CN)(4)]PF(6) and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel polymeric coordination compounds, [Cu(2)(TCNB)(3)](PF(6))(2)(Me(2)CO)(4)( )()(1) and [Cu(2)(TCNB)(3)](PF(6))(2) (2), depending on the solvents used. The crystal structures have been determined by single-crystal X-ray diffraction. Crystal data are as follows. 1: C(21)H(15)N(6)O(2)CuPF(6), monoclinic, P2(1)/a, a = 11.553(4) Å, b = 16.135(7) Å, c = 15.046(3) Å, beta = 108.08(2) degrees, Z = 4. 2: C(15)H(3)N(6)CuPF(6), orthorhombic, Cmcm, a = 28.282(3) Å, b = 10.337(3) Å, c = 16.285(4) Å, Z = 16. In both polymers, copper(I) ions have similar pseudotetrahedral environments and the four coordination sites are fully occupied by the four bridging ligands, two &mgr;(2)-TCNB and two &mgr;(4)-TCNB groups. Polymer 1, obtained in acetone, revealed a two-dimensional zigzag sheet network between copper(I) ions, whereas 2, synthesized in methylethyl ketone, displayed a three-dimensional porous framework with different functional groups (or atom) in different cavities. The redox, magnetic, and conductive behaviors of both complexes are discussed. It is demonstrated that the two complexes give different physicochemical properties.