Long-Range Ruthenium-Amine Electronic Communication through the para-Oligophenylene Wire


The studies of long-range electronic communication are hampered by solubility and potential-splitting issues. A "hybridized redox-asymmetry" method using a combination of organic and inorganic redox species is proposed and exemplified to overcome these two issues. Complexes 1(PF6)-6(PF6) (from short to long in length) with the organic redox-active amine and inorganic cyclometalated ruthenium termini bridged by the para-oligophenylene wire have been prepared. Complex 6 has the longest Ru-amine geometrical distance of 27.85 Å. Complexes 3(PF6) and 4(PF6) show lamellar crystal packing on the basis of a head-to-tail anti-parallelly aligned dimeric structure. Two redox waves are observed for all complexes in the potential region between +0.2 and +0.9 V vs Ag/AgCl. The electrochemical potential splitting is 410, 220, 143, 112, 107, and 105 mV for 1(PF6) through 6(PF6), respectively. Ruthenium (+2) to aminium (N(•+)) charge transfer transitions have been identified for the odd-electron compounds 1(2+)-6(2+) by spectroelectrochemical measurements. The electronic communication between amine and ruthenium decreases exponentially with a decay slope of -0.137 Å(-1). DFT calculations have been performed to complement these experimental results.

DOI: 10.1038/srep13835

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@inproceedings{Shen2015LongRangeRE, title={Long-Range Ruthenium-Amine Electronic Communication through the para-Oligophenylene Wire}, author={Jun-Jian Shen and Yu-Wu Zhong}, booktitle={Scientific reports}, year={2015} }