Strong ferromagnetic interactions in [V(8)O(14)(H(_2)taci)(2)]: an unprecedented large spin ground state for a vanadyl cluster.
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Journal Article↗
Biomedical subjects
Jon Zubieta
Publications and source records attributed to Jon Zubieta.
Non-merohedrally twinned crystals of N,N'-bis(3-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine: an excellent triphenylamine-based hole transporter.
N,N'-Bis(3-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (TPD), C(38)H(32)N(2), crystallizes in the monoclinic space group P2(1) with a pseudo-orthogonal lattice, rather than the previously reported orthorhombic space group P2(1)2(1)2(1) [Kennedy, Smith, Tackley, David, Shankland, Brown & Teat (2002). J. Mater. Chem. 12, 168-172]. The asymmetric unit consists of two independent molecules, A and B, which are arranged along the [100] direction to form vertical layers of alternately stacked A and B molecules. Molecule A shows a great deal of rotational movement in the four terminal aryl rings, resulting in two disordered tolyl groups split over two sites, while molecule B exhibits an almost cis configuration of the two terminal tolyl groups with respect to these ring planes.
Journal Article↗
A metal-mediated dimerization of the ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate.
The title compound, methylene bis[bis(N,N-diethylamino)carbeniumdithiocarboxylate] pentachlorooxorhenium, (C(21)H(42)N(4)S(4))[ReCl(5)O], is the result of an unusual dimerization of the ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate [(Et(2)N)(2)C(2)S(2)] upon reaction with [ReOCl(3)(PPh(3))(2)] in chloroform under reflux conditions. The compound was obtained as a dicationic moiety, with the molecular [ReOCl(5)](2-) anion providing the charge compensation. The planes of the carbenium and thiocarboxylate moieties are nearly perpendicular to one another and the backbone C-C bond length in the N(2)CCS(2) group is the same as a normal C-C single-bond length.
Journal Article↗
Solid state coordination chemistry: structural consequences of variations in tether length in the oxovanadium-copper-bisterpy-[O3P(CH2)nPO3]4- system, n= 1-6 (bisterpy = 2,2':4',4'':2'',2'''-quarterpyridyl-6',6''-di-2-pyridine).
Hydrothermal reactions of Na3VO4, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2 (n = 1-6) yielded a family of materials of the type [Cu2(bisterpy)]4+/VxOy(n-)/[O3P(CH2)nPO3]4-. This family of bimetallic oxides is characterized by an unusual structural diversity. The oxides [[Cu2(bisterpy)]V2O4[O3PCH2PO3H]2] (1), [[Cu2(bisterpy)(H2O)]VO2[O3P(CH2)3PO3][HO3P(CH2)3PO3H2]] (4) and [[Cu2(bisterpy)]V2O4[O3P(CH2)6PO3H]2].2H2O (7.2H2O) are one-dimensional, while [[Cu2(bisterpy)(H2O)2]V2O4[O3P(CH2)2PO3][HO3P(CH2)2PO3H]2] (2), [[Cu2(bisterpy)]V4O8[O3P(CH23PO3]2].4H2O (3.4H2O) and [[Cu2(bisterpy)]V2O4(OH)2[O3P(CH2)4PO3]].4H2O (5.4H2O) are two-dimensional. The V(IV) oxide [[Cu2(bisterpy)]V4O4[O3P(CH2)5PO3H]4].7.3H2O (6.7.3H2O) provides a relatively unusual example of a three-dimensional bimetallic oxide phosphonate. The structures reveal a variety of V/P/O substructures as building blocks.
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Solid state coordination chemistry of oxomolybdenum organoarsonate materials.
The oxomolybdenum-arsonate system was investigated under hydrothermal conditions in the presence of charge-compensating copper(II)-organonitrogen complex cations as secondary building blocks. A series of materials of the Mo/O/As/Cu/ligand family has been prepared and structurally characterized. The architectures of the products reflect the identity of the arsonate component and the organonitrogen ligand, as well as the reaction conditions. The structural versatility of this emerging class of compounds is manifested by the one-dimensional structures of [[Cu(o-phen)(H(2)O)(2)](2)Mo(6)O(18)(O(3)AsOH)(2)] (1), [[Cu(terpy)](2)Mo(4)O(13)H(AsO(4))(2)].2H(2)O (2.2H(2)O), [[Cu(2,2'-bpy)(H(2)O)](2)Mo(6)O(18)(O(3)AsC(6)H(5))(2)].2H(2)O (4.2H(2)O), and [[Cu(o-phen)(H(2)O)](2)[Mo(6)O(18)(O(3)AsC(6)H(5))(2)]].4H(2)O (5.4H(2)O), by the two-dimensional materials [[Cu(2)(tpyprz)(H(2)O)(2)]Mo(6)O(18)(O(3)AsOH)(2)].2H(2)O (3.2H(2)O), [[Cu(terpy)](2)Mo(6)O(18)(O(3)AsC(6)H(5))(2)].H(2)O (6.H(2)O), and [[Cu(2)(tpyprz)]Mo(6)O(18)(O(3)AsC(6)H(5))(2)].2H(2)O (7.2H(2)O), and the molecular clusters [[Cu(2,2'-bpy)(2)](2)Mo(12)O(34)(O(3)AsC(6)H(5))(4)].2.35H(2)O (8.2.35H(2)O) and [Cu(o-phen)(H(2)O)(3)][Cu(o-phen)(2)Mo(12)O(34) (O(3)AsC(6)H(5))(4)].3H(2)O (9.3H(2)O).
Journal Article↗
Solid state coordination chemistry: one-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups.
The hydrothermal reactions of MoO(3), an appropriate Cu(II) source, tetra-2-pyridylpyrazine (tpypyz), and phosphoric acid and/or an organophosphonate yielded a series of organic-inorganic hybrid materials of the copper-molybdophosphonate family. A common feature of the structures is the entrainment within the extended architectures of chemically robust [Mo(5)O(15)(O(3)PR)(2)](4)(-) clusters as molecular building blocks. The cluster is a characteristic feature of the one-dimensional materials [[Cu(2)(tpypyz)(H(2)O)(3)]Mo(5)O(15)(HPO(4))(O(3)PCH(2)CO(2)H)].H(2)O (1.H(2)O) and [[Cu(2)(tpypyz)(H(2)O)]Mo(5)O(15)(O(3)PC(6)H(5))(2)].2H(2)O (2.2H(2)O), the two-dimensional network [[Cu(2)(tpypyz)(H(2)O)(3)]Mo(5)O(15)(HPO(4))(2)].2H(2)O (5.2H(2)O) and the three-dimensional frameworks [[Cu(2)(tpypyz)(H(2)O)(2)]Mo(5)O(15)[O(3)P(CH(2))(n)()PO(3)]].xH(2)O [n = 3, x = 2.25 (6.2.25H(2)O); n = 4, x = 0.33 (7.0.33H(2)O)]. In the case of methylenediphosphonate as the phosphorus component, the unique chelating nature of the ligand precludes formation of the pentamolybdate core, resulting in the chain structures [[Cu(2)(tpypyz)(H(2)O)]Mo(3)O(8) (HO(3)PCH(2)PO(3))(2)].8H(2)O (3.8H(2)O) and [[Cu(2)(tpypyz)(H(2)O)](2)(Mo(3)O(8))(2)(O(3)PCH(2)PO(3))(3)].16.9H(2)O (4.16.9H(2)O). For structures 1-7, the secondary metal-ligand building block is the binuclear [Cu(2)(tpypyz)(H(2)O)(x)](4+) cluster. There is considerable structural versatility as a result of the variability in the number of attachment sites at the phosphomolybdate clusters, the coordination geometry of the Cu(II), which may be four-, five-, or six-coordinate, the extent of aqua ligation, and the participation of phosphate oxygen atoms as well as molybdate oxo groups in bonding to the copper sites. Crystal data: 1.H(2)O, C(26)H(28)N(6)Cu(2)Mo(5)O(28)P(2), monoclinic C2/c, a = 42.497(2) A, b = 10.7421(4) A, c = 20.5617(8) A, beta = 117.178(1) degrees, V = 8350.1(5) A(3), Z = 8; 2.2H(2)O, C(36)H(32)N(6)Cu(2)Mo(5)O(24)P(2), monoclinic P2(1)/c, a = 11.2478(7) A, b = 19.513(1) A, c = 21.063(1) A, beta = 93.608(1) degrees, V = 4613.7(5) A(3), Z = 4; 3.8H(2)O, C(26)H(40)N(6)Cu(2)Mo(3)O(29)P(4), monoclinic C2/c, a = 32.580(2) A, b = 17.8676(9) A, c = 15.9612(8) A, beta = 104.430(1) degrees, V = 8993.3(8) A(3), Z = 8; 4.16.9H(2)O, C(51)H(71.75)Cu(4)Mo(6)N(12)O(51)P(6), monoclinic P2(1)/c, a = 27.929(3) A, b = 12.892(2) A, c = 22.763(3) A, beta = 90.367(2) degrees, V = 8195.7(2) A(3), Z = 4;( )()5.2H(2)O, C(24)H(28)N(6)Cu(2)Mo(5)O(28)P(2), monoclinic P2(1)/n, a = 11.3222(4) A, b = 18.7673(7) A, c = 19.4124(7) A, beta = 98.819(1) degrees, V = 4076.1(3) A(3), Z = 4; 6.2.25H(2)O, C(27)H(28.5)N(6)Cu(2)Mo(5)O(24.25)P(2), monoclinic C2/c, a = 12.8366(5) A, b = 18.4221(8) A, c = 34.326(1) A, beta = 100.546(1) degrees, V = 7980.1(6) A(3), Z = 8; 7.(1)/(3)H(2)O, C(28)H(28.7)N(6)Cu(2)Mo(5)O(23.3)P(2), monoclinic C2/c, a = 12.577(1) A, b = 18.336(1) A, c = 36.476(3) A, beta = 91.929(2) degrees, V = 8407.3 A(3), Z = 8.
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A building block approach to the synthesis of organic-inorganic oxide materials: the hydrothermal synthesis and network structure of [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (tpypyz = tetra-2-pyridylpyrazine).
The hydrothermal reaction of MoO3, [Ni(CH3CO2)2] x 4H2O, tpypyz, ethylenediphosphonic acid and water yields the 2D material [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (1 x 23H2O), constructed from [Mo5O15(O3PCH2CH2PO3)]4- clusters linked in one-dimension through the ethylene tethers of the diphosphonate component; these molybdodiphosphonate chains are in turn linked into a 2D network through the tetranuclear secondary metal-ligand subunit [Ni4(tpypyz)3]8+.
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Ruthenium(III) polyaminocarboxylate complexes: efficient and effective nitric oxide scavengers.
The preparation of two Ru(III) polyaminocarboxylate complexes, AMD6245 and AMD6221, and their nitrosyl analogues, AMD6204, AMD6263, and AMD3689, is described. The compounds are characterized by IR, ES-MS, and (13)C and (15)N NMR spectroscopy where appropriate and cyclic voltammetry. The crystal structures for AMD6245, AMD6263, and AMD3689 are presented. AMD6245 (C(10)H(14)N(2)O(9)Ru) crystallized in the P2(1)/c space group with a = 8.4382(2) A, b = 8.8304(2) A, c = 17.6321(4) A, beta = 99.603(o), V = 1295.3(2) A(3), and Z = 4. AMD6263 (C(10)H(14)N(3)O(10)Ru) crystallized in the P2(1)/c space group with a = 9.9043(4) A, b = 13.1144(3) A, c = 12.0914(4) A, beta = 100.191(o), V = 1545.8(5) A(3), and Z = 4. AMD3689 (C(14)H(24.56)N(4)O(13.28)Ru) crystallized in the P1 space group with a = 8.838(2) A, b = 9.452(3) A, c = 13.419(4) A, alpha = 78.413(6)(o), beta = 75.804(6)(o), gamma = 73.562(6)(o), V = 1031.8(5) A(3), and Z = 2. The reaction of AMD6245 and AMD6221 with nitric oxide is investigated using EPR spectroscopy and stopped flow kinetics. Upon reaction with NO, a linear, diamagnetic [RuNO](6) complex is formed. The substitution reaction of AMD6245 with NO proceeds with a second-order rate constant of 2.24 x 10(7) M(-1) s(-1) at 7.3 degrees C (pH = 7.4; 50 mM phosphate buffer). The substitution reaction of AMD6221 with NO proceeds with a second-order rate constant of 3 x 10(5) M(-1) s(-1) at 20 degrees C (pH = 7.4; 50 mM phosphate buffered saline). The NO scavenging ability was assessed using a RAW264 murine macrophage assay by measuring the difference in nitrite produced between untreated control cells and treated cells. At 100 microM AMD6245 has [NO(2-)] = 12.5 microM less than the untreated cells and AMD6221 has [NO(2-)] = 37.6 microM less than the untreated cells. There is an insignificant difference in the amount of nitrite produced between AMD6263 or AMD3689 treated cells and untreated cells.
Animals↗
Derivatization, complexation, and absolute configurational assignment of chiral primary amines: application of exciton-coupled circular dichroism.
We report here a sensitive method for the determination of the absolute configurations of primary amines using exciton-coupled circular dichroism (ECCD). The method works on a microgram scale by derivatization of chiral amines with quinoline chromophores. Complexation of the chiral ligands with metal ion fixes the geometry of the chromophores, resulting in a twist that is governed by the asymmetric carbon configuration and steric environment of the amine. The absolute configurations of the primary amines can be interpreted from the couplets of the ECCD spectra of the derivatized complexes. Crystal structures, 2D NMR studies, and semiempirical calculations provide structural evidence for our model.
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Crystal-driven distortion of ligands in copper coordination complexes: conformational pseudo-enantiomers.
The ligand in [Cu(6)CH3CN]-(ClO4)2 adopts two conformations that may be described as "pseudo-enantiomers" in that they possess approximately mirror-image molecular helicity, although they differ in the orientation of a single methyl substituent. The two conformations differ in energy as judged by analogy to other compounds studied previously, computation of the relative free energies of formation of the isomers, and measurement of solution circular dichroism spectra. The solid-state structures of both single enantiomer and racemic forms of the complex were determined by X-ray crystallography. In the chiral complex, a quasi-racemate was observed with both pseudo-enantiomeric conformers present in the asymmetric unit. Packing forces induce a higher energy conformation in order to achieve higher apparent symmetry in the solid state. In contrast, the racemic complex only displayed a single conformation corresponding to the lower energy one of the two observed in the single enantiomer structure.
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Bifunctional single amino acid chelates for labeling of biomolecules with the [Tc(CO)(3)](+) and [Re(CO)(3)](+) cores. Crystal and molecular structures of [ReBr(CO)(3)(H(2)NCH(2)C(5)H(4)N)], [Re(CO)(3)[(C(5)H(4)NCH(2))(2)NH]]Br, [Re(CO)(3)[(C(5)H(4)NCH(2))(2)NCH(2)CO(2)H]]Br, [Re(CO)(3)[X(Y)NCH(2)CO(2)CH(2)CH(3)]]Br (X = Y = 2-pyridylmethyl; X = 2-pyridylmethyl, Y = 2-(1-methylimidazolyl)methyl; X = Y = 2-(1-methylimidazolyl)methyl), [ReBr(CO)(3)[(C(5)H(4)NCH(2))NH(CH(2)C(4)H(3)S)]], and [Re(CO)(3)[(C(5)H(4)NCH(2))N(CH(2)C(4)H(3)S)(CH(2)CO(2))]].
The reactions of a series of potentially tridentate ligands, derived from single amino acids or amino acid analogues, with [NEt(4)](2)[ReBr(3)(CO)(3)] have been investigated. The model compounds [Re(CO)(3)Br[(2-pyridylmethyl)NH(2)]] (1) and [Re(CO)(3)[(2-pyridylmethyl)(2)NH]]Br (2) were also prepared and structurally characterized. With ligands possessing two pyridyl appendages, (2-pyridylmethyl)(2)NX (X = -CH(2)CO(2)H, -CH(2)CO(2)Et, -CH(2)CH(2)CO(2)H, -CH(2)CH(2)CO(2)Et, -CH(2)CH(2)CH(2)CH(2)CH(NHCO(2)(t)Bu)CO(2)H), complexes of the type [Re(CO)(3)(ligand)]Br (3-6) were isolated. All possess the fac-[Re(CO)(3)N(3)] coordination geometry in the cationic molecular unit. Similarly, the ligands with the imidazolyl arms (2-pyridylmethyl)[2-(1-methylimidazolyl)methyl]NCH(2)CO(2)Et and [2-(1-methylimidazolyl)methyl](2)NCH(2)CO(2)Et, complexes 7 and 8 of the same [Re(CO)(3)(ligand)]Br type, were prepared. Replacement of one pyridyl arm with a thiophene group yielded the complex [Re(CO)(3)[(2-pyridylmethyl)N(CH(2)CO(2))(2-thiophenemethyl)]] (9), while additional substitution of X = -H for -CH(2)CO(2)H yielded [Re(CO)(3)Br[(2-pyridylmethyl)NH(2-thiophenemethyl)]] (10). In both 9 and 10, the thiophene is uncoordinated and pendant, and the derivatives display fac-[Re(CO)(3)N(2)O] and fac-[Re(CO)(3)N(2)Br] coordination geometries, respectively. Crystal data: C(9)H(8)BrN(2)O(3)Re (1), triclinic P1, a = 8.156(1) A, b = 12.077(1) A, c = 12.945(2) A, alpha = 92.183(3) degrees, beta = 107.848(3) degrees, gamma = 100.955(7) degrees, V = 1185.1(3) A, Z = 4; C(15)H(13)BrN(3)O(3)Re (2), tetragonal P4(1), a = 8.6095(3) A, c = 22.228(1) A, V = 1646.9(1) A(3), Z = 4; C(17)H(14)BrN(3)O(5)Re.CH(3)OH (3), monoclinic P2(1)/m, a = 7.4425(3) A, b = 9.7596(4) A, c = 14.0646(6) A, beta = 97.753(1) degrees, V = 1012.26(7) A(3), Z = 2; C(19)H(19)BrN(3)O(5)Re (4), tetragonal P42(1)c, a = 16.895(3) A, c = 15.042(3) A, V = 4293.7(13) A(3), Z = 8; C(18)H(20)BrN(4)O(5)Re.CH(3)OH.H(2)O (7), monoclinic P2(1)/c, a = 10.2816(4) A, b = 30.386(1) A, c = 14.5810(6) A, beta = 99.868(1) degrees, V = 4488.03(3) A(3), Z = 8; C(17)H(21)BrN(5)O(5)Re.0.5CH(2)Cl(2).0.5H(2)O (8), triclinic P1, a = 11.5363(6) A, b = 13.1898(6) A, c = 16.4933(8) A, alpha = 89.356(1) degrees, beta = 74.907(1) degrees, gamma = 76.216(1) degrees, V = 2349.8(2) A(3), Z = 4; C(16)H(13)N(2)O(5)ReS (9), monoclinic P2(1)/c, a = 17.2072(7) A, b = 8.5853(4) A, c = 11.5607(5) A, beta = 101.73(1) degrees, V = 1672.2(1) A(3), Z = 4; and C(14)H(12)N(2)O(3)BrReS (10), triclinic P1, a = 7.5585(3) A, b = 9.7713(4) A, c = 11.7103(4) A, alpha = 109.566(1) degrees, beta = 98.298(1) degrees, gamma = 100.925(1) degrees, V = 779.73(5) A(3), Z = 2.
Journal Article↗
[Re(III)Cl(3)] core complexes with bifunctional single amino acid chelates.
The reactions of the Re(V) starting material [ReO(PPh(3))(2)Cl(3)] with ligands of the type XN(Y)Z [X = Y = 2-pyridylmethyl, Z = -CH(2)CO(2)Et (L(1)Et), -CH(2)CH(2)CO(2)Et (L(2)Et), -CH(2)CH(2)CH(2)CH(2)CH(NHCO(2)Bu(t))CO(2)H (L(3)H); X = 2-pyridylmethyl, Y = 2-(1-methylimidazolyl)methyl, Z = -CH(2)CO(2)Et (L(4)Et)] yielded the Re(III) trichloride complexes of the type [ReCl(3)(L(n)R)]. The complexes are mononuclear, paramagnetic species with a facial geometry of the chloride ligands. The nitrogen donors of the tridentate L(n)()R ligands complete the distorted octahedral coordination spheres of the complexes. Crystal data: [ReCl(3)(L(1)Et)] (1), monoclinic, C2/m, a = 16.088(3) A, b = 9.980(2) A, c = 12.829(2) A, beta = 91.384(3) degrees, Z = 4, D(calc) = 1.967 g/cm(-)(3); [ReCl(3)(L(4)Et)] (4), monoclinic, C2/c, a = 22.880(1) A, b = 7.4926(4) A, c = 22.560(1) A, beta = 94.186(1) degrees, Z = 8, D(calc) = 2.001 g/cm(-3).
Amino Acids↗
Structural properties of a series of photochromic fluorinated indolylfulgides.
Fluorinated indolylfulgides are a class of photochromic organic compounds that meet many of the requirements for use as optical memory media and optical switches. The X-ray crystal structures of a series of five photochromic fluorinated indolylfulgides have been determined, namely (3Z)-3-[1-(1,2-dimethyl-1H-indol-3-yl)-2,2,2-trifluoroethylidene]-4-(1-methylethylidene)dihydrofuran-2,5-dione (trifluoromethylisopropylideneindolylfulgide), C(19)H(16)F(3)NO(3), (I), (3Z)-3-[1-(1,2-dimethyl-1H-indol-3-yl)-2,2,3,3,3-pentafluoropropylidene]-4-(1-methylethylidene)dihydrofuran-2,5-dione (pentafluoroethylisopropylideneindolylfulgide), C(20)H(16)F(5)NO(3), (II), (3Z)-3-[1-(1,2-dimethyl-1H-indol-3-yl)-2,2,3,3,4,4,4-heptafluorobutylidene]-4-(1-methylethylidene)dihydrofuran-2,5-dione (heptafluoropropylisopropylideneindolylfulgide), C(21)H(16)F(7)NO(3), (III), (3Z)-3-[1-(1,2-dimethyl-1H-indol-3-yl)-2,2,2-trifluoroethylidene]-4-(tricyclo[3.3.1.1(3,7)]decylidene)dihydrofuran-2,5-dione (trifluoromethyladamantylideneindolylfulgide), C(26)H(24)F(3)NO(3), (IV), and (3Z)-3-[1-(1,2-dimethyl-1H-indol-3-yl)-2,2,3,3,4,4,4-heptafluorobutylidene]-4-(tricyclo[3.3.1.1(3,7)]decylidene)dihydrofuran-2,5-dione (heptafluoropropyladamantylideneindolylfulgide), C(28)H(24)F(7)NO(3), (V). The photochromic property of fulgides is based on the photochemically allowed electrocyclic ring closure of a hexatriene system to form a cyclohexadiene. For each fulgide examined, the bond lengths within the hexatriene system alternate between short and long, as expected. Comparing the structures of the five fulgides with each other demonstrates no significant difference in bond lengths, bond angles or dihedral angles within the hexatriene systems. The distance between the bond-forming C atoms at each end of the hexatriene system does vary. Correlations of structural properties with optical properties are addressed.
Adamantane↗
Organic-inorganic hybrid materials: hydrothermal syntheses and structural characterization of bimetallic organophosphonate oxides of the type Mo/Cu/O/RPO(3)(2-)/organoimine.
The hydrothermal reactions of a Cu(II) starting material, a molybdate source, 2,2'-bipyridine or terpyridine, and the appropriate alkyldiphosphonate ligand yield two series of bimetallic organophosphonate hybrid materials of the general types [Cu(n)(bpy)(m)Mo(x)O(y)(H(2)O)(p)[O(3)P(CH(2))(n)PO(3)](z)] and [Cu(n)(terpy)(m)Mo(x)O(y)(H(2)O)(p)[O(3)P(CH(2))(n)PO(3)](z)]. The bipyridyl series includes the one-dimensional materials [Cu(bpy)(MoO(2))(H(2)O)(O(3)PCH(2)PO(3))] (1) and [[Cu(bpy)(2)][Cu(bpy)(H(2)O)](Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)CH(2)PO(3))].H(2)O (5.H(2)O) and the two-dimensional hybrids [Cu(bpy)(Mo(2)O(5))(H(2)O)(O(3)PCH(2)PO(3))].H(2)O (2.H(2)O), [[Cu(bpy)](2)(Mo(4)O(12))(H(2)O)(2)(O(3)PCH(2)CH(2)PO(3))].2H(2)O (3.2H(2)O), and [Cu(bpy)(Mo(2)O(5))(O(3)PCH(2)CH(2)CH(2)PO(3))](4). The terpyridyl series is represented by the one-dimensional [[Cu(terpy)(H(2)O)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)PO(3))].3H(2)O (7.3H(2)O) and the two-dimensional composite materials [Cu(terpy)(Mo(2)O(5))(O(3)PCH(2)PO(3))] (6) and [[Cu(terpy)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)PO(3))] (8). The structures exhibit a variety of molybdate building blocks including isolated [MoO(6)] octahedra in 1, binuclear subunits in 2, 4, and 6, tetranuclear embedded clusters in 3, and the prototypical [Mo(5)O(15)(O(3)PR)(2)](4-) cluster type in 5, 7, and 8. These latter materials exemplify the building block approach to the preparation of extended structures.
Journal Article↗
Ligand influences on copper molybdate networks: the structures and magnetism of [Cu(3,4'-bpy)MoO(4)], [Cu(3,3'-bpy)(0.5)MoO(4)], and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O.
The reactions of a Cu(II) salt, MoO(3), and the appropriate bipyridine ligand yield a series of bimetallic oxides, [Cu(3,4'-bpy)MoO(4)] (1), [Cu(3,3'-bpy)(0.5)MoO(4)] (2), and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O (3.1.5H(2)O). The structures of 1-3 exhibit three-dimensional covalent frameworks, constructed from bimetallic oxide layers tethered by the dipodal organoimine ligands. However, the [CuMoO(4)] networks are quite distinct. For structure 1, the layer consists of corner-sharing [MoO(4)] tetrehedra and [CuN(2)O(3)] square pyramids, while the layer of 2 is constructed from [MoO(4)] tetrehedra and binuclear [Cu(2)O(6)N(2)] units of edge-sharing copper square pyramids. The oxide substructure of 3 consists of [MoO(4)] tetrahedra corner-sharing with tetranuclear clusters of edge-sharing [CuO(5)N] octahedra. Crystal data: C(10)H(8)N(2)O(4)CuMo (1), orthorhombic Pbca, a = 12.4823(6) A, b = 9.1699(4) A, c = 19.5647(9) A, V = 2239.4(1) A(3), Z = 8; C(5)H(4)NO(4)CuMo (2), triclinic P, a = 5.439(1) A, b = 6.814(1) A, c = 10.727(2) A, alpha = 73.909(4)(o), beta = 78.839(4)(o); gamma = 70.389(4)(o); V = 357.6(1) A(3), Z = 2; C(10)H(8)N(2)O(8)Cu(2)Mo(2).3H(2)O 3.1.5H(2)O, triclinic P, a = 7.4273(7) A, b = 9.2314(8) A, c = 13.880(1) A, alpha = 71.411(2)(o), beta = 88.528(2)(o), gamma = 73.650(2)(o), V = 863.4(1) A(3), Z = 2. The magnetic properties of 1-3 arise solely from the presence of the Cu(II) sites, but reflect the structural differences within the bimetallic oxide layers. Compound 1 exhibits magnetic behavior consistent with ferromagnetic chains which couple antiferromagnetically at low temperature. Compound 2 exhibits strong antiferromagnetic dimeric interactions, with the magnetic susceptibility data consistent with the Bleaney-Bowers equation. Similarly, the magnetic susceptibility of 3 is dominated by antiferromagnetic interactions, which may be modeled as a linear S = 1/2 Heisenberg tetramer.
Journal Article↗
Ligand Influences on Copper Cyanide Solid-State Architecture: Flattened and Fused "Slinky", Corrugated Sheet, and Ribbon Motifs in the Copper-Cyanide-Triazolate-Organoamine Family.
A series of novel composite inorganic-organic materials from the copper-cyanide-triazolate-organoamine system have been isolated and structurally characterized. An unusual interpenetrating layered structure type composed of fused and flattened "slinkies", [Cu(6)(CN)(5)(trz)] (1) (trz = triazolate, C(2)N(3)H(2)(-)), a complex corrugated layer structure, [Cu(5)(CN)(3)(trz)(2)(bpy)] (2), and a series of increasingly intricate one-dimensional ribbons, [Cu(3)(CN)(2)(trz)(bpy)], [Cu(3)(CN)(2)(trz)(phen)], and [Cu(4)(CN)(3)(trz)(phen)] (3-5), have been isolated from hydrothermal media. All trz ligands are deprotonated and participate in &mgr;(3)-bridging of Cu sites. An anionic layered compound, [Cu(OH(2))(4)][Cu(4)(CN)(6)] (6), composed of {Cu(6)(CN)(6)} rings with tetraaquacupric dications intercalated into alternate interlamellar spaces, has also been characterized upon the slow evaporation of the mother liquor of 1. The syntheses and structural characterizations of compounds 1-6 by single-crystal X-ray diffraction and FTIR microscopy are discussed in relation to the supramolecular chemistry of other copper cyanide solid-state materials. Crystal data: C(7)H(2)Cu(6)N(8) (1), orthorhombic, Pcca, a = 11.108(2) Å, b = 8.886(2) Å, c = 15.397(3) Å, Z = 4; C(34)H(24)Cu(10)N(22) (2), triclinic, P&onemacr;, a = 9.1183(5) Å, b = 9.9838(6) Å, c = 12.7545(8) Å, alpha = 94.206(1) degrees, beta = 90.492(1) degrees, gamma = 112.534(1) degrees, Z = 1; C(28)H(20)Cu(6)N(14) (3), monoclinic, P2(1)/c, a = 9.7582(1) Å, b = 17.1622(2) Å, c = 9.901(1) Å, beta = 106.869(1) degrees, Z = 2; C(17)H(10)Cu(4)N(8) (4), monoclinic, P2(1)/c, a = 11.590(3) Å, b = 20.555(4) Å, c = 16.158(3) Å, beta = 103.865(5) degrees, Z = 8; C(16)H(10)Cu(3)N(7) (5), triclinic, P&onemacr;, a = 8.542(2) Å, b = 9.802(2) Å, c = 20.439(4) Å, alpha = 82.468(5) degrees, beta = 83.126(5) degrees, gamma = 79.832(5) degrees, Z = 4; C(6)Cu(5)N(6)O(4) (6), monoclinic, P2(1)/n, a = 7.466(1) Å, b = 8.952(2) Å, c = 11.116(2) Å, beta = 92.816(5) degrees, Z = 4.
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Solid-State Coordination Chemistry of Metal Oxides: Hydrothermal Synthesis and Structural Characterization of o-Phenanthroline-Ligated Copper- and Zinc-Molybdenum Oxides.
The hydrothermal chemistry of molybdate with phenanthroline in the presence of M(II) cations was investigated. With Cu(II) starting materials, modifications in reaction conditions yielded the molecular cluster [Cu(o-phen)(2)Mo(4)O(13)] (MOXI-27) and one-dimensional [Cu(o-phen)MoO(4)].H(2)O (MOXI-28). The analogous Zn(II)-containing one-dimensional material [Zn(o-phen)MoO(4)] (MOXI-29) was isolated under conditions similar to those employed for the preparation of MOXI-28. Crystal data: C(24)H(16)CuMo(4)N(4)O(13) (MOXI-27), monoclinic, P2(1)/c, a = 10.5218(3) Å, b = 12.1113(4) Å, c = 22.0125(7) Å, beta = 97.988(1) degrees, Z = 4; C(12)H(10)CuMoN(2)O(5) (MOXI-28), monoclinic, P2(1)/n, a = 14.050(1) Å, b = 5.8818(4) Å, c = 16.227(1) Å, beta = 103.586(1) degrees, Z = 4; C(12)H(8)MoN(2)O(4)Zn (MOXI-29), monoclinic, P2(1)/m, a = 8.7714(7) Å, b = 6.4172(2) Å, c = 10.652(1) Å, beta = 100.702(5) degrees, Z = 2.
Journal Article↗
Synthesis and Characterization of Zinc and Cadmium Compounds with Arenephosphinothiol Ligands. Crystal and Molecular Structures of [Cd(2){2-(Ph(2)PO)C(6)H(4)S}(4)], [Zn{2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)S}(2)], [Cd{2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)S}(2)(CH(3)OH)], and [Zn{PhPO(C(6)H(4)S-2)(2)}(bipy)].
The electrochemical oxidation of a metallic anode (zinc or cadmium) in an acetonitrile solution of a series of arenephosphinothiol ligands, 2-(Ph(2)P)C(6)H(4)SH, 2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)SH, 2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)SH, and PhP(C(6)H(4)SH-2)(2) [abbreviated RP-(SH)(x)(), x = 1 or 2], affords [M(RP-S)(2)] and [M(RP-S(2))], M = Zn, Cd. Adducts of several of these compounds with 1,10-phenanthroline and 2,2'-bipyridine have also been obtained by addition of these coligands to the electrolysis phase. The compounds obtained have been characterized by microanalysis, IR, UV-visible, FAB spectrometry and (1)H, (31)P NMR spectroscopic studies. The compounds, [Cd(2){2-(Ph(2)PO)C(6)H(4)S}(4)]CH(3)CN (1), [Zn{2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)S}(2)] (2), [Cd{2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)S}(2)(CH(3)OH)] (3), and [Zn{PhPO(C(6)H(4)S-2)(2)}(bipy)] (4), have been also characterized by single-crystal X-ray diffraction. Compound 1 is binuclear with a {Cd(2)S(2)} core and distorted trigonal bipyramidal {CdO(2)S(3)} geometry about the Cd sites. Compounds 2, 3, and 4 are mononuclear with distorted tetrahedral {ZnP(2)S(2)}, distorted square pyramidal {CdO(3)S(2)}, and distorted trigonal bipyramidal {ZnON(2)S(2)} geometries, respectively. Crystal data: 1, C(42)H(37)N(3)O(2)P(2)S(2)Cd, triclinic, P&onemacr;, a = 13.5780(2) Å, b = 13.8505(2) Å, c = 13.9526(2) Å, alpha = 106.622(1) degrees, beta = 109.693(1) degrees, gamma = 107.137(1) degrees, V = 2133.30(5) Å(3), Z = 2, 9560 reflections, R = 0.0483; 2, C(46)H(50)N(2)P(2)S(2)Si(2)Zn, monoclinic, C2/c, a = 21.332(4) Å, b = 9.391(2) Å, c = 25.938(5) Å, beta = 113.84(3) degrees, V = 4753(2) Å(3), Z = 4, 2564 reflections, R = 0.0377; 3, C(43)H(48)CdO(3)P(2)S(2)Si(2), triclinic, P&onemacr;, a = 12.1237(4) Å, b = 14.0568(4) Å, c = 15.0938(2) Å, alpha = 70.836(2) degrees, beta = 83.410(2) degrees, gamma = 65.397(2) degrees, V = 2208.7(1) Å(3), Z = 2, 4936 reflections, R = 0.0738; 4, C(29)H(22)Cl(3)N(2)OP(2)S(2)Zn, triclinic, P&onemacr;, a = 8.9556(3) Å, b = 12.7911(4) Å, c = 14.0598(5) Å, alpha = 82.671(1) degrees, beta = 73.140(1) degrees, gamma = 74.113(1) degrees, V = 1480.44(9)(1) Å(3), Z = 2, 3820 reflections, R = 0.0511.
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