ONSET OF BAND-LIKE PROPERTIES IN THE LIGAND-BRIDGED, TRIMERIC CLUSTER ([(PY)2RU3O(OAC)6(PYR)]2[RU3O(OAC)6(CO)])
ONSET OF BAND-LIKE PROPERTIES IN THE LIGAND-BRIDGED, TRIMERIC CLUSTER ([(PY)2RU3O(OAC)6(PYR)]2[RU3O(OAC)6(CO)])
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DOI：
10.1021/ja00505a020
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发表时间：
1979-01-01
影响因子：
15
通讯作者：
MEYER, TJ
中科院分区：
文献类型：
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作者：
BAUMANN, JA;WILSON, ST;MEYER, TJ
通过单体簇合物[Ru30(CH3C02)6(Py)2(Pyr)]+和[Ru30(CH3C02)6(CH30H)2(C0)]反应，合成了配体桥联的三聚簇合物|[(Py)2Ru30(CH3C02)6(C0)]2[Ru30(CH3C02)6(C0)]KPF6)2(py=吡啶，pyr=吡嗪)。电化学研究表明，该三聚体具有超乎寻常的可逆电子转移化学。与组成它的单体单元相比，它的光学和氧化还原性质是很有意义的。当它的总电子含量很低时，例如，在上面提到的2+离子中，它的性质是对于团簇间电子相互作用较弱的孤立团簇单元的预期性质。然而，电化学研究的结果表明，随着电子含量的增加，团簇中心之间的电子耦合增强，一系列紧密间隔的单电子波的出现可能标志着该离散化学体系中出现了带状行为。
The ligand-bridged trimeric cluster|[(py) 2Ru30 (CH3C02) 6 (pyr)] 2 [Ru30 (CH3C02) 6 (C0)] KPF6) 2 (py= pyri-dine, pyr= pyrazine) has been prepared by a reaction between the monomeric clusters [Ru30 (CH3C02) 6 (py) 2 (pyr)]+ and [RU30 (CH3C02) 6 (CH30H) 2 (C0)]. Electrochemical studies show that the trimer has an extraordinary degree of reversible electron-transfer chemistry. Its opticaland redox properties are of interestwhen compared to those of the monomer units which make it up. When its total electron content is low, which is the case, for example, in the 2+ ion mentioned above, its properties are those expected for isolated cluster units where intercluster electronic interactions are weak. However, the results of electrochemicalstudies suggest that as electron content increases, electronic coupling between the cluster sites is enhanced and the appearance of a series of closely spaced, one-electron waves may signal the appearance of band-like behavior in this discrete chemical system.