Synthesis, Crystal Structure and Spectroscopic Properties of an Octanuclear V-S-Cu Cluster {V_2S_6Cu_6}(PPh_3)_6(O)_2·2CH_2Cl_2·CH_3OH with a Metal-sulfur Dodecahedral Cage

A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.

Crystal Structure of an Octanuclear Sandwich Cluster of Silver（I） and 4,4＇-Bis（2,5-dimethylstyryl）biphenyl

Reaction of the oligo（phenylenevinylene） 4,4＇-bis（2,5-dimethylstyryl）biphenyl （bdb） with CF3CO2Ag in benzene gave a novel octanuclear sandwich cluster [Ags（bdb）2（C6H6）2（CF3CO2）8]·2C6H6 （1）. The clusters are packed on each other through strong n-n interactions to form ^1D ＇brick＇ chains, between which the solvated benzene molecules are located. TG analysis showed that cluster 1 could completely liberate the guest benzene molecules at 105℃ and the coordinated benzene molecules at 180 ℃. In solid state, cluster 1 exhibits fluorescence, and the emission band is red-shifted compared with that of free ligand bdb.

新型八核铜配合物乳剂的体内外抗肿瘤作用

目的探讨新型八核铜配合物乳剂(N-Cu)的体内、外抗肿瘤作用。方法采用甲基噻唑基四唑(MTT)法检测不同浓度N-Cu对HT29、HeLa、SGC7901和EC9706肿瘤细胞增殖的影响。利用S180腹水瘤小鼠模型观察不同浓度N-Cu的体内抗肿瘤作用。采用流式细胞仪测定不同浓度N-Cu对S180细胞周期的影响。结果 N-Cu作用4种肿瘤细胞24h后,细胞增殖均受到了不同程度的抑制,且呈浓度依赖性。N-Cu对荷S180小鼠的肿瘤生长有明显的抑制作用。N-Cu能使G0/G1期细胞明显增多,S期细胞减少,细胞被阻滞于G0/G1期,差异具有统计学意义(P<0.05)。结论 N-Cu在体内、外具有抗肿瘤作用。

大核镉硫簇合物的研究 （Ⅱ）两个八核镉硫簇合物的合成与晶体结构

利用ＣＳ_２与镉硫化合物在溶剂中反应产生Ｓ^（２－）来合成大核镉硫簇合物，得到了两个新的大核镉硫簇合物，并测定了其晶体结构，化合物（Ⅰ）为（Ｍｅ_４Ｎ）_２［ＳＣｄ_８（ＳＰｈ）_（１２）Ｃｌ_４］，晶体属立方晶系，空间群Ｐａ３，ａ＝２６．７８２（３）Ａ，Ｖ＝１９２１１（４）Ａ~３，Ｄｃ＝１．７５０ｇ／ｃｍ~３，Ｚ＝８。１６３７个衍射点参与修正，Ｒ＝６．９６％，化合物（Ⅱ）为［Ｃｄ（Ｈ_２Ｏ）_６］［ＳＣｄ_８（ＳＰｈ）_（１２）Ｃｌ_４］，晶体属立方晶系，空间群Ｆ４３ｃ，ａ＝２７．５９７（５）Ａ，Ｖ＝２１４９１（７）Ａ~３，Ｄｃ＝１．６０９ｇ／ｃｍ~３，Ｚ＝８。５６５个衍射点参与修正，Ｒ＝４．９９％。两个化合物都含有八核镉簇阴离子，但它们的正离子不同，对称性也不同。本文还讨论了这一合成方法的机理和特点。