Molecular QCA Cells. 1. Structure and Functionalization of an Unsymmetrical Dinuclear Mixed-Valence Complex for Surface Binding
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- 作者：Zhaohui Li ; Alicia M. Beatty ; and Thomas P. Fehlner
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：September 8, 2003
- 年：2003
- 卷：42
- 期：18
- 页码：5707 - 5714
- 全文大小：198K
- 年卷期：v.42,no.18(September 8, 2003)
- ISSN：1520-510X
文摘
Utilization of binary information encoded in the charge configuration of quantum-dot cells (the quantum-dot cellularautomata, QCA, paradigm) requires molecule-sized dots for room temperature operation. Molecular QCA cells aremixed-valence complexes, and the evaluation and functionalization of an unsymmetrical heterobinuclear, two-dot,Fe-Ru molecular QCA cell is described. The solid state structures of trans-RuCl(dppm)2(C
CFc) (1) (dppm =methylbis(diphenylphosphane), Fc = (
5-C5H5)Fe(5-C5H4)) and mixed-valence [trans-RuCl(dppm)2(CCFc)][BF4](1a) as well as XPS and spectroscopic data suggest class II behavior suitable for the intended application. Utilizationof the trans-Cl position of 1 permits functionalization for surface binding. Two "tailed" complexes of 1, trans-Ru(dppm)2(CCFc)(CCPhOCH3) (2) and trans-[Ru(dppm)2(CCFc)(NCCH2CH2NH2)][PF6] (3), have been preparedand characterized. The solid state structure of 3 and multinuclear NMR experiments define the structures. In addition,the spectroscopic properties of all complexes and their mixed-valence species are used to define the effect of thesubstituent "tail" on mixed-valence properties. Further, the electrochemistry of these compounds permits assessmentof the extent of perturbation of the substituents on the comproportionation constants and overall electrochemicalstability. The complexes possess properties necessary for candidate QCA molecules.
CFc) (1) (dppm =methylbis(diphenylphosphane), Fc = (5-C5H5)Fe(5-C5H4)) and mixed-valence [trans-RuCl(dppm)2(CCFc)][BF4](1a) as well as XPS and spectroscopic data suggest class II behavior suitable for the intended application. Utilizationof the trans-Cl position of 1 permits functionalization for surface binding. Two "tailed" complexes of 1, trans-Ru(dppm)2(CCFc)(CCPhOCH3) (2) and trans-[Ru(dppm)2(CCFc)(NCCH2CH2NH2)][PF6] (3), have been preparedand characterized. The solid state structure of 3 and multinuclear NMR experiments define the structures. In addition,the spectroscopic properties of all complexes and their mixed-valence species are used to define the effect of thesubstituent "tail" on mixed-valence properties. Further, the electrochemistry of these compounds permits assessmentof the extent of perturbation of the substituents on the comproportionation constants and overall electrochemicalstability. The complexes possess properties necessary for candidate QCA molecules.