Electronic conductivity of solid-state, mixed-valent, monolayer-protected Au clusters
Electronic conductivity of solid-state, mixed-valent, monolayer-protected Au clusters
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DOI：
10.1021/ja002367
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发表时间：
2000-11
影响因子：
15
通讯作者：
W. P. Wuelfing;S. J. Green;J. Pietron;D. Cliffel;R. Murray
中科院分区：
文献类型：
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作者：
W. P. Wuelfing;S. J. Green;J. Pietron;D. Cliffel;R. Murray
烷基硫醇盐单层保护的Au团簇（Au MPC）固态膜中的电子电导率σEL通过双分子电子自交换反应发生，其速率常数由（a）电子电荷的核到核隧穿控制沿着烷基硫醇盐链和（B）MPC核心的混合价态（例如，具有不同电子电荷的核的混合物）。的隧道机制表明Au 309（Cn）92 MPC（平均组合物）和n，链硫醇链长，从4到16变化的电子电导率之间的指数关系。电子隧穿系数βn = 1.2/CH 2，或在考虑链硫醇酯链的叉指后，βdis = 0.8 A-1。使用低多分散性Au 140（C6）53 MPC的量化电化学双层充电来制备含有MPC核心电子电荷的明确定义的混合物（例如MPC 0与MPC 1+混合）的溶液。混合价态固态Au 140（C6）53 MPC薄膜的电子电导率
Electronic conductivity, σEL, in solid-state films of alkanethiolate monolayer protected Au clusters (Au MPCs) occurs by a bimolecular, electron self-exchange reaction, whose rate constant is controlled by (a) the core-to-core tunneling of electronic charge along alkanethiolate chains and (b) the mixed valency of the MPC cores (e.g., a mixture of cores with different electronic charges). The tunneling mechanism is demonstrated by an exponential relation between the electronic conductivity of Au309(Cn)92 MPCs (average composition) and n, the alkanethiolate chainlength, which varies from 4 to 16. The electron tunneling coefficient βn = 1.2/CH2 or, after accounting for alkanethiolate chain interdigitation, βdis = 0.8 A-1. Quantized electrochemical double layer charging of low polydispersity Au140(C6)53 MPCs was used to prepare solutions containing well-defined mixtures of MPC core electronic charges (such as MPC0 mixed with MPC1+). Electronic conductivities of mixed-valent, solid-state Au140(C6)53 MPC films ...