Synthesis, structural, and photoluminescence studies of Gd(terpy)(H2O)(NO3)2M(CN)2 (M = Au, Ag) complexes: multiple emissions from intra- and intermolecular excimers and exciplexes

The highly luminescent bimetallic cyanide materials, Gd(terpy)(H(2)O)(NO(3))(2)M(CN)(2) (M = Au, Ag; GdAu and GdAg, respectively) are quick and easy to synthesize under ambient conditions. A characteristic feature exhibited by both solid-state compounds is an intense red emission when excited with UV light. Additionally, GdAu exhibits a broad-band green emission upon excitation in the near UV region. A combination of structural and spectroscopic results for the compounds helps explain the underlying conditions responsible for their unique properties. Single-crystal X-ray diffraction experiments expose their structural features, including the fact that they are isostructural. Crystallographic data for the representative GdAu compound (Mo K(α), λ = 0.71073 ?, T = 290 K): triclinic, space group P ?1, a = 7.5707(3) ?, b = 10.0671(4) ?, c = 15.1260(4) ?, α = 74.923(3)°, β = 78.151(3)°, γ = 88.401(3)°, V = 1089.04(7) ?(3), and Z = 2. Although the compounds crystallize as dimers containing M···M distances smaller than the sum of their van der Waals radii, the Au···Au (3.5054(4) ?) and/or the Ag···Ag (3.6553(5) ?) interactions are relatively weak and are not responsible for the low energy red emission. Rather, the green emission in GdAu presumably originates from the [Au(CN)(2)(-)](2) dimeric excimer, while the [Ag(CN)(2)(-)](2) dimers in GdAg do not display visible emission at either 290 or 77 K. The unusual red emission exhibited by both compounds likely originates from the formation of an excited state exciplex that involves intermolecular π-stacking of 2,2':6',2"-terpyridine ligands. The room-temperature and low-temperature steady-state photoluminescent properties, along with detailed time-dependent, lifetime, and quantum yield spectroscopic data provide evidence regarding the sources of the multiple visible emissions exhibited by these complexes.     

New structural features of unsupported chains of metal ions in luminescent [(NH3)4Pt][Au(CN)2]2 x 1.5(H2O) and related salts

Luminescent [(NH(3))(4)Pt][Au(CN)(2)](2).1.5(H(2)O), which forms from aqueous solutions of [(NH(3))(4)Pt]Cl(2) and K[Au(CN)(2)], crystallizes with extended chains of the two ions with multiple close Pt...Au (3.2804(4) and 3.2794(4) A) and Au...Au (3.2902(5), 3.3312(5), and 3.1902(4) A) contacts. Nonluminescent [(NH(3))(4)Pt][Ag(CN)(2)](2).1.4(H(2)O) is isostructural with [(NH(3))(4)Pt][Au(CN)(2)](2).1.5(H(2)O). Treatment of [(NH(3))(6)Ni]Cl(2) with K[Au(CN)(2)] forms [(NH(3))(2)Ni][Au(CN)(2)](2) in which the [Au(CN)(2)](-) ions function as nitrile ligands toward nickel, which assumes a six-coordinate structure with trans NH(3) ligands. The [Au(CN)(2)](-) ions self-associate into linear columns with close Au...Au contacts of 3.0830(5) A, and pairs of gold ions in these chains make additional but longer (3.4246(5) A) contacts with other gold ions.     

Synthesis, characterization and magnetic properties of four new organically templated metal sulfates [C5H14N2][M(II)(H2O)6](SO4)2, (M(II) = Mn, Fe, Co, Ni)

A series of novel organically templated metal sulfates, [C(5)H(14)N(2)][M(II)(H(2)O)(6)](SO(4))(2) with (M(II) = Mn (1), Fe (2), Co (3) and Ni (4)), have been successfully synthesized by slow evaporation and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, thermogravimetric analysis and magnetic measurements. All compounds were prepared using a racemic source of the 2-methylpiperazine and they crystallized in the monoclinic systems, P2(1)/n for (1, 3) and P2(1)/c for (2,4). Crystal data are as follows: [C(5)H(14)N(2)][Mn(H(2)O)(6)](SO(4))(2), a = 6.6385(10) ?, b = 11.0448(2) ?, c = 12.6418(2) ?, β = 101.903(10)°, V = 906.98(3) ?(3), Z = 2; [C(5)H(14)N(2)][Fe(H(2)O)(6)](SO(4))(2), a = 10.9273(2) ?, b = 7.8620(10) ?, c = 11.7845(3) ?, β = 116.733(10)°, V = 904.20(3) ?(3), Z = 2; [C(5)H(14)N(2)][Co(H(2)O)(6)](SO(4))(2), a = 6.5710(2) ?, b = 10.9078(3) ?, c = 12.5518(3) ?, β = 101.547(2)°, V = 881.44(4) ?(3), Z = 2; [C(5)H(14)N(2)][Ni(H(2)O)(6)](SO(4))(2), a = 10.8328(2) ?, b = 7.8443(10) ?, c = 11.6790(2) ?, β = 116.826(10)°, V = 885.63(2) ?(3), Z = 2. The three-dimensional structure networks for these compounds consist of isolated [M(II)(H(2)O)(6)](2+) and [C(5)H(14)N(2)](2+) cations and (SO(4))(2-) anions linked by hydrogen-bonds only. The use of racemic 2-methylpiperazine results in crystallographic disorder of the amines and creation of inversion centers. The magnetic measurements indicate that the Mn complex (1) is paramagnetic, while compounds 2, 3 and 4, (M(II) = Fe, Co, Ni respectively) exhibit single ion anisotropy.     

Hydrolysis studies on bismuth nitrate: synthesis and crystallization of four novel polynuclear basic bismuth nitrates

Hydrolysis of Bi(NO(3))(3) in aqueous solution gave crystals of the novel compounds [Bi(6)O(4)(OH)(4)(NO(3))(5)(H(2)O)](NO(3)) (1) and [Bi(6)O(4)(OH)(4)(NO(3))(6)(H(2)O)(2)]·H(2)O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(1)/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) ?, b = 13.4298(9) ?, c = 17.8471(14) ?, β = 94.531(6)°, V = 2210.5(3) ?(3); 2, a = 9.0149(3) ?, b = 16.9298(4) ?, c = 15.6864(4) ?, β = 90.129(3)°, V = 2394.06(12) ?(3). Variation of the conditions for partial hydrolysis of Bi(NO(3))(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·4DMSO] (3) and [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·0.5DMSO] (5), upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1? both with two crystallographically independent molecules in the asymmetric unit. The following lattice parameters are observed: 3, a = 20.3804(10) ?, b = 20.3871(9) ?, c = 34.9715(15) ?, α = 76.657(4)°, β = 73.479(4)°, γ = 60.228(5)°, V = 12021.7(9) ?(3); 5, a = 20.0329(4) ?, b = 20.0601(4) ?, c = 34.3532(6) ?, α = 90.196(1)°, β = 91.344(2)°, γ = 119.370(2)°, V = 12025.8(4) ?(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.     

Synthesis and Characterization of a Series of Triethylphosphine-Ligated Pt-Au Cluster Compounds. X-ray Crystal and Molecular Structure of [Pt(AuPEt(3))(9)](NO(3))(3)

The first triethylphosphine-stabilized Pt-Au cluster compounds, [Pt(AuPEt(3))(10)](2+) (2) and [Pt(AuPEt(3))(9)](3+) (3), were prepared by the direct reaction of Pt(PEt(3))(3) with AuPEt(3)NO(3) under a dihydrogen atmosphere. Cluster 2 is the highest-nuclearity homoleptic Pt(AuPR(3))(n)() cluster yet prepared. The reactivity and structures of these clusters are in agreement with the well-established electron-counting arguments. The 18-electron cluster 2 was converted into the 16-electron cluster 3 by oxidation with 2 equiv of ferricinium ion [Fe(eta(5)-C(5)H(5))(2)](+). Cluster 3 was converted into 2 by reduction with H(2) in the presence of [AuPEt(3)](+). Cluster 3 was also observed to cleanly add the 2-electron donors CO and PEt(3) to form the 18-electron clusters [(CO)Pt(AuPEt(3))(9)](3+) (4) and [(PEt(3))Pt(AuPEt(3))(9)](3+) (5), respectively. Single-crystal X-ray diffraction results show that 3 has a flattened, toroidal structure in which the PtAu(9) framework has a Pt-centered, tricapped trigonal prismatic geometry. Crystal data for [Pt(AuPEt(3))(9)](NO(3))(3) is as follows: hexagonal P6(3)/m, a = 15.134(5) ?, c = 23.48(1) ?, V = 4657 ?(3), Z = 2, residuals R = 0.056, and R(w)() = 0.053 for 1489 observed reflections and 81 variables, Mo Kalpha radiation. Compound 3 was found to reversibly add H(2) in solution to form the dihydride cluster [(H)(2)Pt(AuPEt(3))(9)](3+) (6). The equilibrium constant for this addition reaction is 1.1 x 10(3) M(-)(1) (CD(2)Cl(2) solution, 25 degrees C), slightly smaller than that for [Pt(AuPPh(3))(8)](2+). The rate of the addition is also slower than that with [Pt(AuPPh(3))(8)](2+). Cluster 3 is an excellent homogeneous catalyst for H(2)-D(2) equilibration giving a turnover rate for HD production of 0.13 s(-)(1) (nitrobenzene solvent, 30 degrees C, 1 atm). The PEt(3)-containing clusters give similar rates and follow the same general trends previously observed with PPh(3)-ligated clusters. The chemistry of these new clusters is explained by consideration of the steric and electronic properties of the PEt(3) ligand. These new compounds will be useful as models for hydrogen activation by Pt-Au clusters and as precursors for supported Pt-Au catalysts.     

Spectroscopic and magnetic properties of a series of μ-cyano bridged bimetallic compounds of the type M(II)-NC-Fe(III) (M = Mn, Co, and Zn) using the building block [Fe(III)(CN)5imidazole]2-

In this contribution, we describe the preparation and single-crystal X-ray diffraction of a new building block for bimetallic solid state materials. X-ray diffraction data of these complexes indicate that (PPh(4))(2)[Fe(CN)(5)imidazole]·2H(2)O crystallizes in the triclinic space group P1 with a = 9.8108(15) ?, b = 11.1655(17) ?, c = 23.848(4) ?, α = 87.219(2)°, β = 85.573(2)°, γ = 70.729(2)°, and Z = 2, while its precursor Na(3)[Fe(CN)(5)(en)]·5H(2)O crystallizes in the monoclinic space group P2(1)/n with a = 8.3607(7) ?, b = 11.1624(9) ?, c = 17.4233(14) ?, β = 90.1293(9)°, and Z = 4. Spectroscopic and magnetic properties of a series of bimetallic materials were obtained by reaction of the complex [Fe(CN)(5)imidazole](2-) with hydrated transition metal ions [M(H(2)O)(n)](2+) (M = Mn, Co, Zn; n = 4 or 6). The new bimetallic materials obtained are [Co(H(2)O)(2)][Fe(CN)(5)imidazole]·2H(2)O (1), [Mn(CH(3)OH)(2)][Fe(CN)(5)imidazole] (2), Zn[Fe(CN)(5)imidazole]·H(2)O (3), and [Mn(bpy)][Fe(CN)(5)imidazole].H(2)O (4). All of the complexes crystallize in the orthorhombic system. X-ray single-crystal analysis of the compounds identified the Imma space group with a = 7.3558(10) ?, b = 14.627(2) ?, c = 14.909(2) ?, and Z = 4 for 1; the P2(1)2(1)2(1) space group with a = 7.385(5) ?, b = 13.767(9) ?, c = 14.895(10) ?, and Z = 4 for 2; the Pnma space group with a = 13.783(2) ?, b = 7.167(11) ?, c = 12.599(2) ?, and Z = 4 for 3; and the Pnma space group with a = 13.192(3) ?, b = 7.224(16) ?, c = 22.294(5) ?, and Z = 4 for 4. The structures of 1, 2, and 4 consist of two-dimensional network layers containing, as the repeating unit, a cyclic tetramer [M(2)Fe(2)(CN)(4)] (M = Mn, Co). H bonding between the layers in the structure of 1 results in a quasi-three-dimensional network. The structure of 3 was found to be three-dimensional, where all of the cyano ligands are involved in bridging between the metal centers. The bridging character of the cyano is confirmed spectroscopically. The magnetic properties have been investigated for all of the bimetallic systems. Compound 1 shows ferromagnetic behavior with an ordering temperature at 25 K, which is higher than the corresponding Prussian Blue analogue Co(x)[Fe(CN)(6)](y)?·zH(2)O. Compound 2 shows weak ferromagnetic behavior and an interlayer antiferromagnetic character, while 3, as expected, shows paramagnetic character due to the diamagnetic character of Zn(2+). Compound 4 shows antiferromagnetic behavior.     

Metal-metal interactions in heterobimetallic d8-d10 complexes. Structures and spectroscopic investigation of [M'M' '(mu-dcpm)2(CN)2]+ (M' = Pt,Pd; M' ' = Cu,Ag, Au) and related complexes by UV-vis absorption and resonance Raman spectroscopy and ab initio calculations

X-ray structural and spectroscopic properties of a series of heterodinuclear d(8)-d(10) metal complexes [M'M' '(mu-dcpm)(2)(CN)(2)](+) containing d(8) Pt(II), Pd(II), or Ni(II) and d(10) Au(I), Ag(I), or Cu(I) ions with a dcpm bridging ligand have been studied (dcpm = bis(dicyclohexylphosphino)methane; M' = Pt, M' ' = Au 4, Ag 5, Cu, 6; M' ' = Au, M' = Pd 7, Ni 8). X-ray crystal analyses showed that the metal...metal distances in these heteronuclear metal complexes are shorter than the sum of van der Waals radii of the M' and M' ' atoms. The UV-vis absorption spectra of 4-6 display red-shifted intense absorption bands from the absorption spectra of the mononuclear trans-[Pt(phosphine)(2)(CN)(2)] and [M' '(phosphine)(2)](+) counterparts, attributable to metal-metal interactions. The resonance Raman spectra confirmed assignments of (1)[nd(sigma)-->(n + 1)p(sigma)] electronic transitions to the absorption bands at 317 and 331 nm in 4 and 6, respectively. The results of theoretical calculations at the MP2 level reveal an attractive interaction energy curve for the skewed [trans-Pt(PH(3))(2)(CN)(2)-Au(PH(3))(2)(+)] dimer. The interaction energy of Pt(II)-Au(I) was calculated to be ca. 0.45 ev.     

Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2)

The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) ?, b = 17.4045(2) ?, c = 55.2353(1) ?, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) ?(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2)-D(2) equilibration is general for 18-electron hydrido Pt-AuPPh(3) clusters.     

Heterobimetallic lanthanide-gold coordination polymers: structure and emissive properties of isomorphous [(n)Bu4N]2[Ln(NO3)4Au(CN)2] 1-D chains

A new series of lanthanide-containing dicyanoaurate coordination polymers, [(n)Bu(4)N](2)[Ln(NO(3))(4)Au(CN)(2)] (Ln = Nd, Eu, Gd or Tb), were synthesized and structurally characterized. They form an isomorphous series, crystallizing in the space group I2(1)2(1)2(1). The structure is composed of a one dimensional zigzag of Ln-N-C-Au-C-N-Ln chains with no intra- or inter-chain aurophilic interactions. The series is related to and can be described as a reduced dimensionality analogue of the previously studied Ln[Au(CN)(2)](3)·3H(2)O. Unlike the Ln[Au(CN)(2)](3)·3H(2)O series, there is no efficient energy transfer between dicyanoaurate and the lanthanide metal centers in the complexes and they essentially act as two separate emissive chromophores.     

Gold(I) Complexes with the nido-Diphosphino Ligand [7,8-(Ph(2)P)(2)-7,8-C(2)B(9)H(10)](-). Preparation of the First Metallocarborane Complex of this Ligand. Crystal Structures of [Au{(PPh(2))(2)C(2)B(9)H(10)}(PPh(3))].CH(2)Cl(2) and [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2){(PPh(2))(2)(CH(2))(3)}].3Me(2)CO

The reaction of [AuCl(PR(3))] with [1,2-(Ph(2)P)(2)-1,2-C(2)B(10)H(10)] in refluxing ethanol proceeds with partial degradation (removal of a boron atom adjacent to carbon) of the closo species to give [Au{(PPh(2))(2)C(2)B(9)H(10)}(PR(3))] [PR(3) = PPh(3) (1), PPh(2)Me (2), PPh(2)(4-Me-C(6)H(4)) (3), P(4-Me-C(6)H(4))(3) (4), P(4-OMe-C(6)H(4))(3) (5)]. Similarly, the treatment of [Au(2)Cl(2)(&mgr;-P-P)] with [1,2-(Ph(2)P)(2)-1,2-C(2)B(10)H(10)] under the same conditions leads to the complexes [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2)(&mgr;-P-P)] [P-P = dppe = 1,2-bis(diphenylphosphino)ethane (6), dppp = 1,3-bis(diphenylphosphino)propane (7)], where the dppe or dppp ligands bridge two gold nido-diphosphine units. The reaction of 1 with NaH leads to removal of one proton, and further reaction with [Au(PPh(3))(tht)]ClO(4) gives the novel metallocarborane compound [Au(2){(PPh(2))(2)C(2)B(9)H(9)}(PPh(3))(2)] (8). The structure of complexes 1 and 7 have been established by X-ray diffraction. [Au{(PPh(2))(2)C(2)B(9)H(10)}(PPh(3))] (1) (dichloromethane solvate) crystallizes in the monoclinic space group P2(1)/c, with a = 17.326(3) ?, b = 20.688(3) ?, c = 13.442(2) ?, beta = 104.710(12) degrees, Z = 4, and T = -100 degrees C. [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2)(&mgr;-dppp)] (7) (acetone solvate) is triclinic, space group P&onemacr;, a = 13.432(3) ?, b = 18.888(3) ?, c = 20.021(3) ?, alpha = 78.56(2) degrees, beta = 72.02(2) degrees, gamma = 73.31(2) degrees, Z = 2, and T = -100 degrees C. In both complexes the gold atom exhibits trigonal planar geometry with the 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate(1-) acting as a chelating ligand.     

Crystal structures of Au2 complex and Au25 nanocluster and mechanistic insight into the conversion of polydisperse nanoparticles into monodisperse Au25 nanoclusters

We previously reported a size-focusing conversion of polydisperse gold nanoparticles capped by phosphine into monodisperse [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) nanoclusters in the presence of phenylethylthiol. Herein, we have determined the crystal structure of [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) nanoclusters and also identified an important side-product-a Au(I) complex formed in the size focusing process. The [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) cluster features a vertex-sharing bi-icosahedral core, resembling a rod. The formula of the Au(I) complex is determined to be [Au(2)(PPh(3))(2)(SC(2)H(4)Ph)](+) by electrospray ionization (ESI) mass spectrometry, and its crystal structure (with SbF(6)(-) counterion) reveals Au-Au bridged by -SC(2)H(4)Ph and with terminal bonds to two PPh(3) ligands. Unlike previously reported [Au(2)(PR(3))(2)(SC(2)H(4)Ph)](+) complexes in the solid state, which exist as tetranuclear complexes (i.e., dimers of [Au(2)(PR(3))(2)(SC(2)H(4)Ph)](+) units) through a Au···Au aurophilic interaction, in our case we found that the [Au(2)(PPh(3))(2)(SC(2)H(4)Ph)](+) complex exists as a single entity, rather than being dimerized to form a tetranuclear complex. The observation of this Au(I) complex allows us to gain insight into the intriguing conversion process from polydisperse Au nanoparticles to monodisperse Au(25) nanoclusters.     

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) ?, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) ?(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) ?, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) ?(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).     

Syntheses, characterization, and luminescence of Pt II-M I (M = Cu, Ag, Au) heterometallic complexes by incorporating Pt(diimine)(dithiolate) with [M2(dppm)2]2+ (dppm = Bis(diphenylphosphino)methane)

Reaction of Pt(diimine)(edt) (edt = 1,2-ethanedithiolate) with M(2)(dppm)(2)(MeCN)(2)(2+) (dppm = bis(diphenylphosphino)methane) gave heterotrinuclear complexes [PtCu(2)(edt)(mu-SH)(dppm)(3)](ClO(4)) (11) and [PtCu(2)(diimine)(2)(edt)(dppm)(2)](ClO(4))(2) (diimine = 2,2'-bpyridine (bpy), 12; 4,4'-dibutyl-2,2'-bipyridine (dbbpy), 13; phenanthroline (phen), 14; 5-bromophenanthroline (brphen), 15) when M = Cu(I). The reaction, however, afforded tetra- and trinuclear complexes [Pt(2)Ag(2)(edt)(2)(dppm)(2)](SbF(6))(2) (17) and [PtAu(2)(edt)(dppm)(2)](SbF(6))(2) (21) when M = Ag(I) and Au(I), respectively. The complexes were characterized by elemental analyses, electrospray mass spectroscopy, (1)H and (31)P NMR, IR, and UV-vis spectrometry, and X-ray crystallography for 14, 17, and 18. The Pt(II)Cu(I)(2) heterotrinuclear complexes 11-15 exhibit photoluminescence in the solid states at 298 K and in the frozen acetonitrile glasses at 77 K. It is likely that the emission originates from a ligand-to-metal charge transfer (dithiolate-to-Pt) (3)[p(S) --> d(Pt)] transition for 11 and from an admixture of (3)[d(Cu)/p(S)-pi(diimine)] transitions for 12-16. The Pt(II)(2)Ag(I)(2) heterotetranuclear complexes 17 and 18 are nonemissive in the solid states and in solutions at 298 K but show photoluminescence at 77 K. The Pt(II)Au(I)(2) heterotrinuclear complexes 19-21, however, are luminescent at room temperature in the solid state and in solution. Compounds 19 and 20 afford negative solvatochromism associated with a charge transfer from an orbital of a mixed metal/dithiolate character to a diimine pi orbital.     

Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(mu-S)2(P-P)2] [P-P=2 x PPh3, Ph2P(CH2)3PPh2

The normally robust monoalkylated complexes [Pt(2)(mu-S)(mu-SR)(PPh(3))(4)](+) can be activated towards further alkylation. Dialkylated complexes [Pt(2)(mu-SR)(2)(P-P)(2)](2+) (P-P=2 x PPh(3), Ph(2)P(CH(2))(3)PPh(2)) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4'-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph(2)P(CH(2))(3)PPh(2) or dppp] which enhances the nucleophilicity of the {Pt(2)(mu-S)(2)} core. This strategy led to the activation of [Pt(2)(mu-S)(mu-SR)(PPh(3))(4)](+) towards R-X as well as isolation and crystallographic elucidation of [Pt(2)(mu-SC(10)H(10)N)(2)(PPh(3))(4)](PF(6))(2) (2a), [Pt(2)(mu-SCH(2)C(O)C(6)H(4)C(6)H(5))(2)(PPh(3))(4)](PF(6))(2) (2b), and a range of functionalized-thiolato bridged complexes such as [Pt(2)(mu-SR)(2)(dppp)(2)](PF(6))(2) [R= -CH(2)C(6)H(5) (8a), -CH(2)CHCH(2) (8b) and -CH(2)CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt(2)(mu-S)(2)(P-P)(2)], thereby guiding the bench-top synthesis of some products observed spectroscopically.     

Contribution of disulfide S2(2-) anions to the crystal and electronic structures in ternary sulfides, Ba12In4S19, Ba4M2S8 (M=Ga, In)

Three semiconducting ternary sulfides have been synthesized from the mixture of elements with about 20% excess of sulfur (to establish oxidant rich conditions) by solid-state reactions at high temperature. Ba(12)In(4)S(19) ≡ (Ba(2+))(12)(In(3+))(4)(S(2-))(17)(S(2))(2-), 1, crystallizes in the trigonal space group R ?3 with a = 9.6182(5) ?, b = 9.6182(5) ?, c = 75.393(7) ?, and Z = 6, with a unique long period-stacking structure of a combination of monometallic InS(4) tetrahedra, linear dimeric In(2)S(7) tetrahedra, disulfide S(2)(2-) anions, and isolated sulfide S(2-) anions that is further enveloped by Ba(2+) cations. Ba(4)In(2)S(8) ≡ (Ba(2+))(4)(In(3+))(2)(S(2-))(6)(S(2))(2-), 2, crystallizes in the triclinic space group P ?1? with a = 6.236(2) ?, b = 10.014(4) ?, c = 13.033(5) ?, α = 104.236(6)°, β = 90.412(4)°, γ = 91.052(6)°, and Z = 2. Ba(4)Ga(2)S(8) ≡ (Ba(2+))(4)(Ga(3+))(2)(S(2-))(6)(S(2))(2-), 3, crystallizes in the monoclinic P2(1)/c with a = 12.739(5) ?, b = 6.201(2) ?, c = 19.830(8) ?, β = 104.254(6)° and Z = 4. Compounds 2 and 3 represent the first one-dimensional (1D) chain structure in ternary Ba/M/S (M = In, Ga) systems. The optical band gaps of 1 and 3 are measured to be around 2.55 eV, which agrees with their yellow color and the calculation results. The CASTEP calculations also reveal that the disulfide S(2)(2-) anions in 1-3 contribute mainly to the bottom of the conduction bands and the top of valence bands, and thus determine the band gaps.     

New vanadium selenites: centrosymmetric Ca2(VO2)2(SeO3)3(H2O)2, Sr2(VO2)2(SeO3)3, and Ba(V2O5)(SeO3), and noncentrosymmetric and polar A4(VO2)2(SeO3)4(Se2O5) (A = Sr2+ or Pb2+)

Five new vanadium selenites, Ca(2)(VO(2))(2)(SeO(3))(3)(H(2)O)(2), Sr(2)(VO(2))(2)(SeO(3))(3), Ba(V(2)O(5))(SeO(3)), Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), have been synthesized and characterized. Their crystal structures were determined by single crystal X-ray diffraction. The compounds exhibit one- or two-dimensional structures consisting of corner- and edge-shared VO(4), VO(5), VO(6), and SeO(3) polyhedra. Of the reported materials, A(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) (A = Sr(2+) or Pb(2+)) are noncentrosymmetric (NCS) and polar. Powder second-harmonic generation (SHG) measurements revealed SHG efficiencies of approximately 130 and 150 × α-SiO(2) for Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), respectively. Piezoelectric charge constants of 43 and 53 pm/V, and pyroelectric coefficients of -27 and -42 μC/m(2)·K at 70 °C were obtained for Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), respectively. Frequency dependent polarization measurements confirmed that the materials are not ferroelectric, that is, the observed polarization cannot be reversed. In addition, the lone-pair on the Se(4+) cation may be considered as stereo-active consistent with calculations. For all of the reported materials, infrared, UV-vis, thermogravimetric, and differential thermal analysis measurements were performed. Crystal data: Ca(2)(VO(2))(2)(SeO(3))(3)(H(2)O)(2), orthorhombic, space group Pnma (No. 62), a = 7.827(4) ?, b = 16.764(5) ?, c = 9.679(5) ?, V = 1270.1(9) ?(3), and Z = 4; Sr(2)(VO(2))(2)(SeO(3))(3), monoclinic, space group P2(1)/c (No. 12), a = 14.739(13) ?, b = 9.788(8) ?, c = 8.440(7) ?, β = 96.881(11)°, V = 1208.8(18) ?(3), and Z = 4; Ba(V(2)O(5))(SeO(3)), orthorhombic, space group Pnma (No. 62), a = 13.9287(7) ?, b = 5.3787(3) ?, c = 8.9853(5) ?, V = 673.16(6) ?(3), and Z = 4; Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), orthorhombic, space group Fdd2 (No. 43), a = 25.161(3) ?, b = 12.1579(15) ?, c = 12.8592(16) ?, V = 3933.7(8) ?(3), and Z = 8; Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), orthorhombic, space group Fdd2 (No. 43), a = 25.029(2) ?, b = 12.2147(10) ?, c = 13.0154(10) ?, V = 3979.1(6) ?(3), and Z = 8.     

Refined crystal structure and idealized structure of mixed-valent Eu4F5(CN2)2: transition possible

The new europium fluoride carbodiimide Eu(4)F(5)(CN(2))(2) was synthesized by solid state reaction from mixtures of EuF(3) and Li(2)(CN(2)) at 700 °C. The crystal structure as refined by single crystal X-ray diffraction (P ?42(1)c, no. 114, a = 16.053(1) ?, c = 6.5150(6) ?, Z = 8) reveals three crystallographically distinct [N═C═N](2-) ions in the structure of mixed-valent Eu(4)F(5)(CN(2))(2). The presence of one Eu(3+) and three Eu(2+) per formula unit Eu(4)F(5)(CN(2))(2) is confirmed by magnetic measurements and (151)Eu-Mo?ssbauer spectroscopy. The arrangement of Eu ions and gravity centers of [NCN](2-) ions in the structure of Eu(4)F(5)(CN(2))(2) follow the motif formed by atoms in the CuAl(2)-type structure. A possible high-symmetry structure of Eu(4)F(5)(CN(2))(2) is discussed on the basis of a group-subgroup scheme.     

Synthesis, characterization, and structure-property relationships in two new polar oxides: Zn2(MoO4)(SeO3) and Zn2(MoO4)(TeO3)

Two new noncentrosymmetric (NCS) polar oxide materials, Zn(2)(MoO(4))(AO(3)) (A = Se(4+) or Te(4+)), have been synthesized by hydrothermal and solid-state techniques. Their crystal structures have been determined, and characterization of their functional properties (second-harmonic generation, piezoelectricity, and polarization) has been performed. The isostructural materials exhibit a three-dimensional network consisting of ZnO(4), ZnO(6), MoO(4), and AO(3) polyhedra that share edges and corners. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation indicate the materials exhibit moderate SHG efficiencies of 100 × and 80 × α-SiO(2) for Zn(2)(MoO(4))(SeO(3)) and Zn(2)(MoO(4))(TeO(3)), respectively. Particle size vs SHG efficiency measurements indicate the materials are type 1 non-phase-matchable. Converse piezoelectric measurements resulted in d(33) values of ～14 and ～30 pm/V for Zn(2)(MoO(4))(SeO(3)) and Zn(2)(MoO(4))(TeO(3)), respectively, whereas pyroelectric measurements revealed coefficients of -0.31 and -0.64 μC/m(2) K at 55 °C for Zn(2)(MoO(4))(SeO(3)) and Zn(2)(MoO(4))(TeO(3)), respectively. Frequency-dependent polarization measurements confirmed that all of the materials are nonferroelectric; that is, the macroscopic polarization is not reversible, or "switchable". Infrared, UV-vis, thermogravimetric, and differential thermal analysis measurements were also performed. First-principles density functional theory (DFT) electronic structure calculations were also done. Crystal data: Zn(2)(MoO(4))(SeO(3)), monoclinic, space group P2(1) (No. 4), a = 5.1809(4) ?, b = 8.3238(7) ?, c = 7.1541(6) ?, β = 99.413(1)°, V = 305.2(1) ?(3), Z = 2; Zn(2)(MoO(4))(TeO(3)), monoclinic, space group P2(1) (No. 4), a = 5.178(4) ?, b = 8.409(6) ?, c = 7.241(5) ?, β = 99.351(8)°, V = 311.1(4) ?(3), Z = 2.     

Syntheses and structural analyses of variable-stoichiometric Au-Pt-Ni carbonyl/phosphine clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2, with ligation-induced site-specific Pt/Ni substitutional disorder within butterfly-based Pt3(Pt(1-x)Ni(x))Au2 and Pt2(Pt(2-y)Ni(y))Au2 core-geometries

In ongoing attempts of directed synthesis of high-nuclearity Au-Pt carbonyl/phosphine clusters with [Ni6(CO)12]2- used as reducing agent and CO source, we have isolated and characterized two new closely related variable-stoichiometric trimetallic clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1) and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2). Their M4Au2 cores may be envisioned as substitutional disordered butterfly-based M4Au2 frameworks (M = Pt/Ni) formed by connections of the two basal M(B) atoms with both (Au-Au)-linked Au(PPh3) moieties. Based upon low-temperature CCD X-ray diffraction studies of eight crystals obtained from different samples, ligation-induced site-specific Pt/Ni substitutional disorder (involving formal insertion of Ni in place of Pt) in a given crystal was found to occur only at the one OC-attached basal M(B) site in 1 or at both OC-attached basal M(B) sites in 2 corresponding to a crystal composite of the Pt3(Pt(1-x)Ni(x))Au2 core in 1 or of the Pt2(Pt(2-y)Ni(y))Au2 core in 2; the Ph3P-attached M(B) site (M(B) = Pt) in 1 and two wingtip M(w) sites (M(w) = Pt) in 1 and 2 were not substitutionally disordered. The resulting variable stoichiometry of the M4Au2 core in 1 may be viewed as a crystal composite of two superimposed individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1a) and Pt3Ni(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1b), in the averaged unit cell of a given crystal. Likewise, 2 represents the crystal-averaged composite of three individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2a), Pt3Ni(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2b), and Pt2Ni2(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2c). Formal Ni substitution for Pt at only the basal M(B) site(s) in the four crystal composites each of 1 and 2 was found to vary widely from 17% to 79% Ni in 1 and from 21% to 95% Ni in 2. Nevertheless, reasonably close Pt/Ni occupancy factors were found within each of the four pairs of composite crystals selected from samples obtained from duplicate syntheses. Both 1 and 2 may be formally derived from the electronically equivalent classic butterfly Pt4(mu2-CO)5(PPh3)4 cluster by replacement of its bridging mu2-CO ligand spanning the basal M(B)-M(B) edge with two one-electron donating (Au-Au)-linked AuPPh3 moieties along with the substitution of a terminal CO in place of one or both M(B)-attached PPh3 ligands in 1 and 2, respectively; site-specific Pt/Ni substitutional disorder occurs only at the CO-attached M(B) sites. The variable-stoichiometric 1 and 2 re also electronically equivalent and geometrically related to the crystal-ordered butterfly-based Pt4(mu2-CO)4(PR3)4(mu3-HgX)2 clusters (R3 = Ph3, MePh2; X = CF3, Br, I).     

Electronic excited states of [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm= bis(dimethylphosphine)methane)

We present studies of the resonance Raman and electronic luminescence spectra of the [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm = bis(dimethylphosphine)methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about approximately 300 nm. The resonance Raman spectra confirm the assignment of the 256 nm absorption band to a (1)(dsigma --> psigma) transition, a metal-metal-localized transition, in that nu(Au-Au) and overtones of it are strongly enhanced. A resonance Raman intensity analysis of the spectra associated with the 256 nm absorption band gives the ground-state and excited-state nu(Au-Au) stretching frequencies to be 79 and 165 cm(-1), respectively, and the excited-state Au-Au distance is calculated to decrease by about 0.1 A from the ground-state value of 3.05 A. The approximately 300 nm absorption displays a different enhancement pattern, in that resonance-enhanced Raman bands are observed at 103 and 183 cm(-1) in addition to nu(Au-Au) at 79 cm(-1) The compound exhibits intense, long-lived luminescence (in room-temperature CH(3)CN, for example, tau = 0.70 micros, phi(emission) = 0.037) with a maximum at 550-600 nm that is not very medium-sensitive. We conclude, in agreement with an earlier proposal of Mason (Inorg. Chem. 1989, 28, 4366-4369), that the lowest-energy, luminescent excited state is not (3)(dsigma --> psigma) but instead derives from (3)(d(x2-y2,xy --> psigma) excitations. We compare the Au(I)-Au(I) interaction shown in the various transitions of the [Au(2)(dmpm)(3)](ClO(4))(2) tribridged compound with previous results for solvent or counterion exciplexes of [Au(2)(dcpm)(2)](2+) salts (J. Am. Chem. Soc. 1999, 121, 4799-4803; Angew. Chem. 1999, 38, 2783-2785; Chem. Eur. J. 2001, 7, 4656-4664) and for planar, mononuclear Au(I) triphosphine complexes. It is proposed that the luminescent state in all of these cases is very similar in electronic nature.