Controlled Assembly Based on Multibridging Thiolate Ligands: New Polymeric Silver(I) Complexes with One-Dimensional Chain and Three-Dimensional Network Structures.
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Biomedical subjects
Jiaxi Lu
Publications and source records attributed to Jiaxi Lu.
Syntheses and Characterizations of the Novel Dodecanuclear Heterobimetallic Cage Clusters: [Et(4)N](2)[(M(2)Cu(2)S(2)O(2)edt(2))(3)(&mgr;(6)-S(2))].CH(2)Cl(2) (M = Mo, W; edt = (-)SC(2)H(4)S(-)).
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Syntheses and Characterizations of a Series of Tetradecanuclear Molybdenum(Tungsten)/Copper/Sulfur Heterobimetallic Cluster Compounds.
Using sulfide ion to substitute the weakly copper(I)-philic ligands of MS(4)(-)(n)()(2)(-)O(n)()/Cu(+) compounds, (M = Mo, W; n = 0, 1), we have prepared and characterized four novel tetradecanuclear clusters having the general formula [(n-Bu)(4)N](4)[M(4)Cu(10)S(16)E(2)E']H(2)O, (M = Mo, E = E' = O for complex 1; M = W, E = (1)/(2)O + (1)/(2)S, E' = O, for complex 2; M = Mo, E = S, E' = (1)/(2)O + (1)/(2)S for complex 3; M = W, E = E' = S, for complex 4). Crystal structures of compounds 1-4 were determined; they are isomorphous and crystallized in the orthorhombic space group Pna2(1), with a = 26.6997(2) Å, b = 19.3133(4) Å, c = 21.4577(4) Å, V = 11064.9(3) Å(3), Z = 4 for [(n-Bu)(4)N](4)[Mo(4)Cu(10)S(18)O].H(2)O (3) and with a = 26.8141(8) Å, b = 19.4412(6) Å, c = 21.4039(5) Å, V = 11157.8(5) Å(3), Z = 4 for [(n-Bu)(4)N](4)[W(4)Cu(10)S(19)].H(2)O (4). The cluster cores have approximate sigma symmetry. The anions 1-4 may be viewed as consisting of one incomplete cubane-like Cu(3)MS(3)E fragment, one trigonal prism-type Cu(3)MS(4), and two butterfly-type Cu(2)MS(3)E' fragments, bridged by two &mgr;(3)-S and one &mgr;(4)-S atoms. There are two (&mgr;(3)-S)Cu(3) configurations in the compounds. Infrared, Raman, and UV/vis spectra of the above compounds are discussed, and the main absorption bands are assigned. (95)Mo NMR spectra and cylic voltammograms are investigated and compared with those of other compounds, (95)Mo NMR spectra show that in the solution there are three kinds of coordination environments of Mo in complexes 1 and 3, and cyclic voltammograms indicate that complexes 1-4 have irreversible electrochemical reductions.
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The Heterobimetallic Polymeric Zigzag Chain [(W(4)S(16)Ag(4))(4-)](n) Derived from the Linear Chain [(WS(4)Ag)(-)](n): Synthesis, Characterization, and Structure of [W(4)S(16)Ag(4).2Ca(DMSO)(6)](n) (DMSO = Dimethyl Sulfoxide).
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Heterobimetallic Clusters of Copper(I) with Trithiotungstate and Trithiomolybdate. Synthesis and Characterization of the Octanuclear Clusters [Et(4)N](4)[M(4)Cu(4)S(12)O(4)] (M = Mo, W) and the Dodecanuclear Clusters [M(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (M = Mo, W; TMEN = N,N,N',N'-Tetramethylethylenediamine).
Synthetic methods for [Et(4)N](4)[W(4)Cu(4)S(12)O(4)] (1), [Et(4)N](4)[Mo(4)Cu(4)S(12)O(4)] (2), [W(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (3), and [Mo(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (4) are described. [Et(4)N](2)[MS(4)], [Et(4)N](2)[MS(2)O(2)], Cu(NO(3))(2).3H(2)O, and KBH(4) (or Et(4)NBH(4)) were used as starting materials for the synthesis of 1 and 2. Compounds 3 and 4 were produced by reaction of [Et(4)N](2)[WOS(3)], Cu(NO(3))(2).3H(2)O, and TMEN and by reaction of [Me(4)N](2)[MO(2)O(2)S(8)], Cu(NO(3))(2).3H(2)O, and TMEN, respectively. Crystal structures of compounds 1-4 were determined. Compounds 1 and 2 crystallized in the monoclinic space group C2/c with a = 14.264(5) Å, b = 32.833(8) Å, c = 14.480(3) Å, beta = 118.66(2) degrees, V = 5950.8(5) Å(3), and Z = 4 for 1 and a = 14.288(5) Å, b = 32.937(10) Å, c = 14.490(3) Å, beta = 118.75(2) degrees, V = 5978.4(7) Å(3), and Z = 4 for 2. Compounds 3 and 4 crystallized in the trigonal space group P3(2)21 with a = 13.836(6) Å, c = 29.81(1) Å, V = 4942(4) Å(3), and Z = 3 for 3 and a = 13.756(9) Å, c = 29.80(2) Å, V = 4885(6) Å(3), and Z = 3 for 4. The cluster cores have approximate C(2v) symmetry. The anions of 1 and 2 may be viewed as consisting of two butterfly-type [CuMOS(3)Cu] fragments bridged by two [MOS(3)](2-) groups. Eight metal atoms in the anions are arranged in an approximate square configuration, with a Cu(4)M(4)S(12) ring structure. Compounds 3 and 4 can be considered to consist of one [M(4)Cu(4)S(12)O(4)](4-) (the anions of 1 and 2) unit capped by Cu(TMEN)(+) groups on each M atom; the Cu(TMEN)(+) groups extend alternately up and down around the Cu(4)M(4) square. The electronic spectra of the compounds are dominated by the internal transitions of the [MOS(3)](2-) moiety. (95)Mo NMR spectral data are investigated and compared with those of other compounds.
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