Electronic conductivity of solid-state, mixed-valent, monolayer-protected Au clusters

被引:280
作者
Wuelfing, WP [1 ]
Green, SJ [1 ]
Pietron, JJ [1 ]
Cliffel, DE [1 ]
Murray, RW [1 ]
机构
[1] Univ N Carolina, Kenan Labs Chem, Chapel Hill, NC 27599 USA
关键词
D O I
10.1021/ja002367+
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Electronic conductivity, sigma (EL), 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 Au-309(C-n)(92) MPCs (average composition) and n, the alkanethiolate chainlength, which varies from 4 to 16. The electron tunneling coefficient beta (n) = 1.2/CH2 or, after accounting for alkanethiolate chain interdigitation, beta (dis) = 0.8 Angstrom (-1). Quantized electrochemical double layer charging of low polydispersity Au-140(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 Au-140(C6)(53) MPC films cast from such solutions are proportional to the concentration product [MPC0][MPC1+], and give a MPC0/1+ electron self-exchange rate constant of ca. 10(10) M-1 s(-1).
引用
收藏
页码:11465 / 11472
页数:8
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