Mixed-valent diruthenium diphosphonate with kagomé structure

This paper reports the first example of diruthenium phosphonate with kagomé structure, namely, [NH3(CH2)4NH3][Ru2(hedpH(0.5))2].2H2O (hedp = 1-hydroxyethylidenediphosphonate). The compound contains kagomé layers that are linked by very strong hydrogen bonds into a nanoscale kagomé structure. Ferromagnetic interactions are mediated between the paramagnetic diruthenium units.     

Novel layered ruthenium diphosphonate containing a mixed valent diruthenium paddlewheel core

This paper reports the synthesis and crystal structure of a novel mixed valence ruthenium(II,III) compound, (NH(4))(3)Ru(2)(hedp)(2).2H(2)O (1), where hedp represents 1-hydroxyethylidenediphosphonate. It has a two-dimensional structure in which the paddlewheel diruthenium(II,III) units of Ru(2)(hedp)(2) are cross-linked through the phosphonate groups. The layers are stacked along the [100] direction with strong intra- and interlayer hydrogen bonds. Primary magnetic results are presented.     

Lanthanide diruthenium(II,III) compounds showing layered and PtS-type open framework structures

Two types of lanthanide diruthenium phosphonate compounds, based on the mixed-valent metal-metal bonded paddlewheel core of Ru(2)(hedp)(2)(3-) [hedp = 1-hydroxyethylidenediphosphonate, CH(3)C(OH)(PO(3))(2)], have been prepared with the formulas Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)2].5.5H(2)O (1.Ln, Ln = La, Ce) and Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)(2)].8H(2)O (2.Ln, Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er). In both types, each Ru(2)(hedp)2(H2O)23- unit is linked by four Ln(3+)ions through four phosphonate oxygen (OP) atoms and vice versa. The geometries of the {LnO(P4)} group, however, are different in the two cases. In 1.Ln, the geometry of {LnO(P4)} is closer to a distorted plane, and thus a square-grid layer structure is found. In 2.Ln, the geometry of {LnO(P4)} is better described as a distorted tetrahedron; hence, a unique PtS-type open-framework structure is observed. The channels generated in structures 2.Ln are filled with water aggregates with extensive hydrogen-bond interactions. The magnetic and electrochemical properties are also investigated.     

Syntheses, structures, and magnetic properties of mixed-valent diruthenium(II,III) diphosphonates with discrete and one-dimensional structures

Four mixed-valent ruthenium diphosphonates, namely, Na(4)[Ru(2)(hedp)(2)X]x16H(2)O [X = Cl (1), Br (2)], K(3)[Ru(2)(hedp)(2)(H(2)O)(2)]x6H(2)O (3), and Na(7)[Ru(2)(hedp)(2)Fe(CN)(6)]x24H(2)O (4), where hedp represents 1-hydroxyethylidenediphosphonate [CH(3)C(OH)(PO(3))(2)](4-), were synthesized and structurally characterized. Compounds 1, 2, and 4 show linear chain structures in which the mixed-valent [Ru(2)(hedp)(2)](3-) dimers are linked by X(-) or [Fe(CN)(6)](4-) bridges. Compound 3 contains discrete species of [Ru(2)(hedp)(2)(H(2)O)(2)](3-) where the axial positions of [Ru(2)(hedp)(2)](3-) paddlewheel are terminated by water molecules. Magnetic studies show that significant antiferromagnetic exchanges are mediated between the [Ru(2)(hedp)(2)](3-) (S = 3/2) units through halide bridges in compounds 1 and 2.     

Zinc diphosphonates templated by organic amines: syntheses and characterizations of [NH3(CH2)2NH3]Zn(hedpH2)2*2H2O and [NH3(CH2)nNH3(CH2)nNH3]Zn2(hedpH)2*2H2O (n=4,5,6) (hedp=1-hydroxyethylidenediphophonate)

Four new zinc diphosphonate compounds with formulas [NH(3)(CH(2))(2)NH(3)]Zn(hedpH(2))(2).2H(2)O, 1, [NH(3)(CH(2))(n)()NH(3)]Zn(2)(hedpH)(2).2H(2)O, (n = 4, 2; n = 5, 3; n = 6, 4) (hedp = 1-hydroxyethylidenediphosphonate) have been synthesized under hydrothermal conditions at 110 degrees C and in the presence of alkylenediamines NH(2)(CH(2))(n)()NH(2) (n = 2, 4, 5, 6). Crystallographic data for 1: monoclinic, space group C2/c, a = 24.7422(15), b = 5.2889(2), c = 16.0338(2) A, beta = 117.903(1) degrees, V = 1856.17(18) A(3), Z = 4; 2: monoclinic, space group P2(1)/n, a = 5.4970(3), b = 12.1041(6), c = 16.2814(12) A, beta = 98.619(5) degrees, V = 1071.07(11) A(3), Z = 2; 3: monoclinic, space group P2(1)/n, a = 5.5251(2), b = 12.5968(3), c = 16.1705(5) A, beta = 99.182(1) degrees, V = 1111.02(6) A(3), Z = 2; 4: triclinic, space group P-1, a = 5.4785(2), b = 14.1940(5), c = 16.0682(6) A, alpha = 81.982(2) degrees, beta = 89.435(2) degrees, gamma = 79.679(2) degrees, V = 1217.11(8) A(3), Z = 2. In compound 1, two of the phosphonate oxygens are protonated. The metal ions are bridged by the hedpH(2)(2-) groups through three of the remaining four phosphonate oxygens, forming a one-dimensional infinite chain. The protonated ethylenediamines locate between the chains in the lattice. In compounds 2-4, only one phosphonate oxygen is protonated. Compounds 2 and 3 have a similar three-dimensional open-network structure composed of [Zn(2)(hedpH)(2)](n) double chains with strong hydrogen bonding interactions between them, thus generating channels along the [100] direction. The protonated diamines and water molecules reside in the channels. Compound 4 contains two types of [Zn(2)(hedpH)(2)](n) double chains which are held together by strong hydrogen bonds, forming a two-dimensional network. The interlayer spaces are occupied by the [NH(3)(CH(2))(6)NH(3)](2+) cations and water molecules. The significant difference between structures 2-4 is also featured by the coordination geometries of the zinc atoms. The geometries of those in 2 can be described as distorted octahedral, and those in 3 as distorted square pyramidal. In 4, two independent zinc atoms are found, each with a distorted octahedral and a tetrahedral geometry, respectively.     

Metal-metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

The complexes [(H3N)5Ru(II)(mu-NC)Mn(I)Lx]2+, prepared from [Ru(OH2)(NH3)5]2+ and [Mn(CN)L(x)] {L(x) = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5Ru(III)(mu-NC)Mn(I)Lx]3+; the osmium(III) analogues [(H3N)5Os(III)(mu-NC)Mn(I)Lx]3+ were prepared directly from [Os(NH3)5(O3SCF3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H3N)5Ru(III)(mu-NC)Mn(I)(PPh3)(NO)(eta-C5H4Me)][PF6]3.2Me2CO.1.5Et2O, [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)(dppm)2-trans][PF6]3.5Me2CO and [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)2{P(OEt)3}(dppm)-trans][PF6]3.4Me2CO, between the amine groups (the H-bond donors) at the Ru(III) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors).     

One-dimensional cobalt diphosphonates exhibiting weak ferromagnetism and field-induced magnetic transitions

This paper reports two new cobalt phosphonate compounds [NH3(CH2)nNH3]Co2(hedpH)2.2H2O [n = 4 (1), 5 (2)], where hedp is (1-hydroxyethylidene)diphosphonate [CH3C(OH)(PO3)2]. Both contain ladderlike chains with the same composition [Co2(hedpH)2](n)(2n-), where edge-shared [CoO6] octahedra are each bridged by O-P-O units. The chains are linked by very strong hydrogen bonds to form a three-dimensional open network with channels in which the diammonium counterions and lattice water reside. Magnetic studies reveal dominant antiferromagnetic interactions between the Co centers within the chain in both compounds. The field dependent magnetization confirms the occurrence of the field-induced magnetic transitions, with the critical fields ca. 25 kOe for 1 and 27.5 kOe for 2, respectively. In the case of compound 2, weak ferromagnetism is also observed at very low temperatures, possibly arising from spin canting of the antiferromagnetically coupled Co(II) ions in the chain. Crystal data: 1, monoclinic, P2(1)/c, a = 5.4868(8), b = 12.9116(18), and c = 15.251(2) A, beta = 98.843(2) degrees, V = 1067.6(3) A(3), Z = 2; 2, monoclinic, P2(1)/c, a = 5.4757(7), b = 12.7740(16), and c = 15.794(2) A, beta = 98.797(2) degrees, V = 1091.7(2) A(3), Z = 2.     

Field-induced magnetic transitions in metal phosphonates with ladderlike chain structures: (NH3C6H4NH3)M2(hedpH)2.H2O [M = Fe, Co, Mn, Zn; hedp = C(CH3)(OH)(PO3)2

This paper reports the syntheses and characterization of four isomorphous compounds (NH(3)C(6)H(4)NH(3))M(2)(hedpH)(2).H(2)O [M = Fe (1), Co (2), Mn (3), Zn (4); hedp = C(CH(3))(OH)(PO(3))(2)]. Each contains two crystallographically different kinds of {M(2)(hedpH)(2)}(n) double chains, where the {M(2)(mu-O)(2)} dimer units are connected by O-P-O bridges. The double chains are connected through extensive hydrogen bonds, hence generating a three-dimensional supramolecular network. The temperature-dependent magnetic susceptibility measurements show dominant antiferromagnetic interactions in compounds 1-3, mediated through the mu-O and/or O-P-O bridges between the metal(II) centers. The magnetization measurements reveal that compounds 1-3 experience field-induced magnetic transitions at low temperatures.     

Synthesis and characterization of ethylbis(2-pyridylethyl)amineruthenium complexes and two different types of C-H bond cleavage at an ethylene arm

Ruthenium complexes bearing ethylbis(2-pyridylethyl)amine (ebpea), which has flexible -C(2)H(4)- arms between the amine and the pyridyl groups and coordinates to a metal center in facial and meridional modes, have been synthesized and characterized. Three trichloro complexes, fac-[Ru(III)Cl(3)(ebpea)] (fac-[1]), mer-[Ru(III)Cl(3)(ebpea)] (mer-[1]), and mer-[Ru(II)Cl(3){η(2)-N(C(2)H(5))(C(2)H(4)py)═CH-CH(2)py}] (mer-[2]), were synthesized using the Ru blue solution. Formation of mer-[2] proceeded via a C-H activation of the CH(2) group next to the amine nitrogen atom of the ethylene arm. Reduction reactions of fac- and mer-[1] afforded a triacetonitrile complex mer-[Ru(II)(CH(3)CN)(3)(ebpea)](PF(6))(2) (mer-[3](PF(6))(2)). Five nitrosyl complexes fac-[RuX(2)(NO)(ebpea)]PF(6) (X = Cl for fac-[4]PF(6); X = ONO(2) for fac-[5]PF(6)) and mer-[RuXY(NO)(ebpea)]PF(6) (X = Cl, Y = Cl for mer-[4]PF(6); X = Cl, Y = CH(3)O for mer-[6]PF(6); X = Cl, Y = OH for mer-[7]PF(6)) were synthesized and characterized by X-ray crystallography. A reaction of mer-[2] in H(2)O-C(2)H(5)OH at room temperature afforded mer-[1]. Oxidation of C(2)H(5)OH in H(2)O-C(2)H(5)OH and i-C(3)H(7)OH in H(2)O-i-C(3)H(7)OH to acetaldehyde and acetone by mer-[2] under stirring at room temperature occurred with formation of mer-[1]. Alternative C-H activation of the CH(2) group occurred next to the pyridyl group, and formation of a C-N bond between the CH moiety and the nitrosyl ligand afforded a nitroso complex [Ru(II)(N(3))(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([8]) in reactions of nitrosyl complexes with sodium azide in methanol, and reaction of [8] with hydrochloric acid afforded a corresponding chloronitroso complex [Ru(II)Cl(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([9]).     

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.     

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz)-derived [Ru(II)(tptz)(acac)(CH3CN)]+ and mixed-valent [(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(CH3CN)]+

Mononuclear [Ru(II)(tptz)(acac)(CH3CN)]ClO4 ([1]ClO4) and mixed-valent dinuclear [(acac)2Ru(III){(mu-tptz-Eta+)-}Ru(II)(acac)(CH3CN)]ClO4 ([5]ClO4; acac = acetylacetonate) complexes have been synthesized via the reactions of Ru(II)(acac)2(CH3CN)2 and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), in 1:1 and 2:1 molar ratios, respectively. In [1]ClO4, tptz binds with the Ru(II) ion in a tridentate N,N,N mode (motif A), whereas in [5]ClO4, tptz bridges the metal ions unsymmetrically via the tridentate neutral N,N,N mode with the Ru(II) center and cyclometalated N,C- state with the Ru(III) site (motif F). The activation of the coordinated nitrile function in [1]ClO4 and [5]ClO4 in the presence of ethanol and alkylamine leads to the formation of iminoester ([2]ClO4 and [7]ClO4) and amidine ([4]ClO4) derivatives, respectively. Crystal structure analysis of [2]ClO4 reveals the formation of a beautiful eight-membered water cluster having a chair conformation. The cluster is H-bonded to the pendant pyridyl ring N of tptz and also with the O atom of the perchlorate ion, which, in turn, makes short (C-H- - - - -O) contacts with the neighboring molecule, leading to a H-bonding network. The redox potentials corresponding to the Ru(II) state in both the mononuclear {[(acac)(tptz)Ru(II)-NC-CH3]ClO4 ([1]ClO4) > [(acac)(tptz)Ru(II)-NH=C(CH3)-OC2H5]ClO4 ([2]ClO4) > [(acac)(tptz)Ru(II)-NH2-C6H4(CH3)]ClO4 ([3]ClO4) > [(acac)(tptz)Ru(II)-NH=C(CH3)-NHC2H5]ClO4 ([4]ClO4)} and dinuclear {[(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(NC-CH3)]ClO4 ([5]ClO4), [(acac)2Ru(III){(mu-tptz-H+(N+-O-)2)-}Ru(II)(acac)(NC-CH3)]ClO4 ([6]ClO4), [(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(NH=C(CH3)-OC2H5)]ClO4 ([7]ClO4), and [(acac)2Ru(III){(mu-tptz-Eta+)-}Ru(II)(acac)(NC4H4N)]ClO4 ([8]ClO(4))} complexes vary systematically depending on the electronic nature of the coordinated sixth ligands. However, potentials involving the Ru(III) center in the dinuclear complexes remain more or less invariant. The mixed-valent Ru(II)Ru(III) species ([5]ClO4-[8]ClO4) exhibits high comproportionation constant (Kc) values of 1.1 x 10(12)-2 x 10(9), with substantial contribution from the donor center asymmetry at the two metal sites. Complexes display Ru(II)- and Ru(III)-based metal-to-ligand and ligand-to-metal charge-transfer transitions, respectively, in the visible region and ligand-based transitions in the UV region. In spite of reasonably high K(c) values for [5]ClO4-[8]ClO4, the expected intervalence charge-transfer transitions did not resolve in the typical near-IR region up to 2000 nm. The paramagnetic Ru(II)Ru(III) species ([5]ClO4-[8]ClO4) displays rhombic electron paramagnetic resonance (EPR) spectra at 77 K (g approximately 2.15 and Deltag approximately 0.5), typical of a low-spin Ru(III) ion in a distorted octahedral environment. The one-electron-reduced tptz complexes [Ru(II)(tptz.-)(acac)(CEta3CN)] (1) and [(acac)2Ru(III){(mu-tptz-Eta+).2-}Ru(II)(acac)(CH3CN)] (5), however, show a free-radical-type EPR signal near g = 2.0 with partial metal contribution.     

Tautomerization of methyldiazene to formaldehyde-hydrazone in ruthenium and osmium complexes

Mixed-ligand hydrazine complexes [M(CO)(RNHNH2)P4](BPh4)2 (1, 2) [M = Ru, Os; R = H, CH3, C6H5; P = P(OEt)3] with carbonyl and triethyl phosphite were prepared by allowing hydride [MH(CO)P4]BPh4 species to react first with HBF4.Et2O and then with hydrazines. Depending on the nature of the hydrazine ligand, the oxidation of [M(CO)(RNHNH2)P4](BPh4)2 derivatives with Pb(OAc)4 at -30 C gives acetate [M(kappa1-OCOCH3)(CO)P4]BPh4 (3a), phenyldiazene [M(CO)(C6H5N=NH)P4](BPh4)2 (3c, 4c), and methyldiazene [M(CO)(CH3N=NH)P4](BPh4)2 (3b, 4b) derivatives. Methyldiazene complexes 3b and 4b undergo base-catalyzed tautomerization of the CH3N=NH ligand to formaldehyde-hydrazone NH2N=CH2, giving the [M(CO)(NH2N=CH2)P4](BPh4)2 (5, 6) derivatives. Complexes 5 and 6 were characterized spectroscopically and by the X-ray crystal structure determination of the [Ru(CO)(NH2N=CH2)[P(OEt)3]4](BPh4)2 (5) derivative. Acetone-hydrazone [M(CO)[NH2N=C(CH3)2]P4](BPh4)2 (7, 8) complexes were also prepared by allowing hydrazine [M(CO)(NH2NH2)P4](BPh4)2 derivatives to react with acetone.     

配合物[NH3(CH2)4NH3]Co(hedpH2)(H2O)2的水热合成与表征(hedpH4=1-羟亚乙基二膦酸)

采用水热合成法以丁二胺作为模板剂合成了钴的有机二膦酸超分子化合物[NH3(CH2)4NH3]Co(hedpH2)2(H2O)2 [hedpH4 = 1-羟亚乙基二膦酸, CH3C(OH)(PO3H2)2]。用元素分析、红外光谱、紫外-可见光谱、热重分析以及单晶结构解析对其进行了表征。该化合物的化学式为:C8H30N2CoO16P4,Mr = 593.15,晶体属单斜晶系,空间群C2/c,晶胞参数a = 16.128(2), b = 12.427(1), c = 12.610(2) ? b = 121.389(9), V = 2157.3(4) 3, Z = 4, Dc = 1.826 g/cm3, m(MoKa) = 1.172 mm-1, F(000) = 1228。结构用直接法解出,最终偏离因子R = 0.0285, wR = 0.0747。该化合物的结构包含单核的Co(hedpH2)2- 阴离子,阴离子之间通过氢键连结形成具有空隙的三维超分子骨架结构,双质子化的丁二胺分子位于空隙中。     

Barrel- and crown-shaped dodecanuclear copper(II) cages built from phosphonate, pyrazole, and hydroxide ligands

The reaction of Cu(ClO4)2. 6H2O with t-BuP(O)(OH)2 and 3,5-(CF3)2PzH in the presence of triethylamine afforded the dodecanuclear cage ([Et3NH]2[Cu12(mu-3,5-(CF3)2Pz)6(mu3-OH)6(mu-OH)3(mu3-t-BuPO3)2(mu6-t-BuPO3)3][t-BuPO2OH][C6H5CH3]2) (2). The molecular structure of this cage revealed that it possesses a barrel-shaped architechture. The cage structure is built by the cumulative coordination action of phosphonate, hydroxide, and pyrazolyl ligands. A similar reaction involving Cu(NO3)2. 3H2O, t-BuP(O)(OH)2, 3,5-dimethylpyrazole, and triethylamine afforded another dodecanuclear cage [Cu12(mu-DMPz)8(eta1-DMPzH)2(mu4-O)2(mu3-OH)4(mu3- t-BuPO3)4].3MeOH (3). The latter is crown-shaped and is built by the coordination of pyrazole, pyrazolyl, phosphonate, hydroxide, oxide, and methanol ligands. Both of the dodecanuclear cages are efficient nucleases in the presence of magnesium monoperoxyphthalate.     

New star-shaped trinuclear Ru(II) polypyridine complexes of imidazo[4,5-f][1,10]phenanthroline derivatives: syntheses, characterization, photophysical and electrochemical properties

A series of new star-shaped trinuclear Ru(II) complexes of imidazo[4,5-f][1,10]phenanthroline derivatives, [{Ru(bpy)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (6), [{Ru(phen)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (7), [{Ru(bpy)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (8), and [{Ru(phen)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (9) [mes(1,4-phO-Izphen)(3) (4) = 2,4,6-tri methyl-1,3,5-tris(4-oxymethyl-1-yl(1H-imidazo-2-yl-[4,5-f][1,10]phenanthroline)phenyl)benzene and (mes(1,2-phO-Izphen)(3) (5) = 2,4,6-trimethyl-1,3,5-tris(2-oxymethyl-1-yl(1H-imidazo-2-yl[4,5-f][1,10]phenanthroline)phenyl)benzene] have been synthesized and characterized. Their photophysical and electrochemical properties have also been studied. The core molecule, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (1) and the trialdehyde intermediate, 2,4,6-trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene (2) are characterized by single crystal X-ray diffraction: triclinic, P1[combining macron]. The complexes 6-9 exhibit Ru(II) metal centered emission at 618, 601, 615, and 605 nm, respectively, in fluid solution at room temperature. The emission profile and emission maxima are similar and independent of the excitation wavelength for each complex. The complexes 6-9 undergo metal centered oxidation and the E(1/2) values for the Ru(II)/Ru(III) redox couples are 1.33, 1.34, 1.35, and 1.35 V versus Ag/Ag(+), respectively, which are cathodically shifted with respect to that of the mononuclear complex [Ru(bpy)(2)(PIP)](2+) (PIP = 2-phenylimidazo[4,5-f][1,10]phenanthroline). The study demonstrates the versatility of the highly symmetric trinucleating imidazo[4,5-f][1,10]phenanthroline-based core ligands 4 and 5 in forming trinuclear Ru(II) complexes.     

Structural diversity of the oxovanadium organodiphosphonate system: a platform for the design of void channels

The hydrothermal reactions of a vanadium source, an appropriate diphosphonate ligand, and water in the presence of HF provide a series of compounds with neutral V-P-O networks as the recurring structural motif. When the {O3P(CH2)(n)PO3}4- diphosphonate tether length n is 2-5, metal-oxide hybrids of type 1, [V2O2(H2O){O3P(CH2)(n)PO3}] x xH2O, are isolated. The type 1 oxides exhibit the prototypical three-dimensional (3-D) "pillared" layer architecture. When n is increased to 6-8, the two-dimensional (2-D) "pillared" slab structure of the type 2 oxides [V2O2(H2O)4{O3P(CH2)6PO3}] is encountered. Further lengthening of the spacer to n = 9 provides another 3-D structure, type 3, constructed from the condensation of pillared slabs to give V-P-O double layers as the network substructure. When organic cations are introduced to provide charge balance for anionic V-P-O networks, oxides of types 4-7 are observed. For spacer length n = 3, a range of organodiammonium cations are accommodated by the same 3-D "pillared" layer oxovanadium diphosphonate framework in the type 4 materials [H3N(CH2)(n)NH3][V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [n = 2, x = 6 (4a); n = 3, x = 3 (4b); n = 4, x = 2 (4c); n = 5, x = 1 (4d); n = 6, x = 0.5 (4e); n = 7, x = 0 (4f)] and [H3NR]y[V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [R = -CH2(NH3)CH2CH3, y = 1, x = 0 (4g); R = -CH3, n = 2, x = 3 (4h); R = -CH2CH3, y = 2, x = 1 (4i); R = -CH2CH2CH3, y = 2, x = 0 (4j); cation = [H2N(CH2CH3)2], y = 2, x = 0 (4k)]. These oxides exhibit two distinct interlamellar domains, one occupied by the cations and the second by water of crystallization. Furthermore, as the length of the cation increases, the organodiammonium component spills over into the hydrophilic domain to displace the water of crystallization. When the diphosphonate tether length is increased to n = 5, structure type 5, [H3N(CH2)2NH3][V4O4(OH)2(H2O){O3P(CH2)5PO3}2] x H2O, is obtained. This oxide possesses a 2-D "pillared" network or slab structure, similar in gross profile to that of type 2 oxides and with the cations occupying the interlamellar domain. In contrast, shortening the diphosphonate tether length to n = 2 results in the 3-D oxovanadium organophosphonate structure of the type 7 oxide [H3N(CH2)5NH3][V3O3{O3P(CH2)2PO3}2]. The ethylenediphosphonate ligand does not pillar V-P-O networks in this instance but rather chelates to a vanadium center in the construction of complex polyhedral connectivity of 7. Substitution of piperazinium cations for the simple alkyl chains of types 4, 5, and 7 provides the 2-D pillared layer structure of the type 6 oxides, [H2N(CH2CH2)NH2][V2O2{O3P(CH)(n)PO3H}2] [n = 2 (6a); n = 4 (6b); n = 6 (6c)]. The structural diversity of the system is reflected in the magnetic properties and thermal behavior of the oxides, which are also discussed.     

Synthesis of new copper cyanide complexes via the transformation of organonitrile to inorganic cyanide

Hydrothermal reaction of diaminomaleonitrile and copper salts under different conditions resulted in copper cyanide coordination polymers {[Cu(H 2O)(NH 3) 4][Cu 3(CN) 5].H 2O} n ( 1), {(CH 3) 4N[Cu(H 2O)(NH 3) 4][Cu 4(CN) 7]} n ( 2), and {(CH 3OH 2) 2[Cu 2(CN) 3]} n ( 3). 1 and 2 are new mixed-valence Cu(I,II), two 3D organic-inorganic molecular framework complexes that exhibit ionic inclusion. 3 is an open copper cyanide framework hosting a guest molecule. Cyanides in 1, 2, and 3 are produced by in situ C-C bond cleavage of diaminomaleonitrile, and then the remaining product is oxidized to form an oxalate group. The potential porosity of the hydrated coordination polymer 3 was estimated using a computational method based on Connolly's algorithm.     

N,N''''-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4,4''''-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O的晶体结构和磁学性质

该文报道了N,N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH_2,[(C7H5N2)CH2]2NCH2PO3H2}的2个镍化合物Ni2(bbimp)2(4,4′-bipy)(H2O)2·2H2O(1)和[Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O(2)。化合物1是4,4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni2(bbimp)2(H2O)2]双核分子与2个中性的[Ni(bbimp)(H2O)2]单核分子。双核分子单元中的2个Ni!离子被2个膦酸氧桥连。在化合物2中,膦酸氧桥连的2个Ni!离子之间存在铁磁性相互作用。     

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.     

Intra and intermolecular magnetic interactions in a series of dinuclear Cu(II)/hxta complexes [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: correlation of magnetic properties with geometry

Nine dinuclear copper(II) complexes with hxta5- ligands [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: [Cu2(MeO-hxtaH)(H2O)2] x 4H2O (1), [Na(micro-H2O)2(H2O)6][Cu2(Cl-hxta)(H2O)3]2 x 6H2O (2), [Cu(H2O)6][Cu2(Me-hxta)(H2O)2](NO3) x 2H2O (3), [Cu2(R-hxtaH)(H2O)3] x 3H2O [R = Cl (4), CH3 (5), and MeO (6)], [Cu2(MeO-hxtaH2)(micro-X)(CH3OH)] x 3CH3OH [X = Cl (7), Br (8)] and K5Na(micro-H2O)10[Cu2(micro-CO3)(Me-hxta)]2 x 4H2O (9), have been synthesized and structurally characterized. In complexes 4-7, the dinuclear units are linked via novel pairwise supramolecular interactions involving the ligand carboxylate groups. The intra- and intermolecular magnetic interactions have been quantified, and the coupling constants have been related to the structural geometries.