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Issue 5, 2011
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Dual [proton]/[hole] mixed valence in a molecular metal: balancing chemical activity in the solid state by tapping into a molecular hole reservoir

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Abstract

We report on the synthesis, the layered triclinic P[1 with combining macron] crystal structure, band structure and Fermi surface analysis and preliminary transport and ESR data of β-(EDT-TTF-I2)2(1+x)˙+[HO2C–CH[double bond, length as m-dash]CH–CO2](1−x)[O2C–CH[double bond, length as m-dash]CH–CO2]x, a metallic radical cation salt of the nominal, mono-deprotonated π-conjugated dicarboxylate anion of fumaric acid with a metal–insulator transition at ca. 70 K and conclude that the system is doped, that is, a fraction of the fumarates are further deprotonated to their dianion forms. It is shown that the actual number of protons required within the extended fumarate network to effectively balance the chemical activity at the nuclei/solution interface during crystal growth is compensated by tapping into the HOMO bands serving as a molecular hole reservoir such that the compound formulation and structure remain intact. A dual [proton]/[hole] mixed-valence is thereby revealed and defined as the duality between the modulation of the electrostatic potential of the environment, the incommensurate number and the physics of migrating holes within a molecular system.

Graphical abstract: Dual [proton]/[hole] mixed valence in a molecular metal: balancing chemical activity in the solid state by tapping into a molecular hole reservoir

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Publication details

The article was received on 01 Sep 2010, accepted on 08 Nov 2010 and first published on 09 Dec 2010


Article type: Paper
DOI: 10.1039/C0JM02897E
Citation: J. Mater. Chem., 2011,21, 1516-1522
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    Dual [proton]/[hole] mixed valence in a molecular metal: balancing chemical activity in the solid state by tapping into a molecular hole reservoir

    Y. Lakhdar, C. Mézière, L. Zorina, M. Giffard, P. Batail, E. Canadell, P. Auban-Senzier, C. Pasquier, D. Jérome, B. Náfrádi and L. Fórró, J. Mater. Chem., 2011, 21, 1516
    DOI: 10.1039/C0JM02897E

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