An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se)

André Deluzet, Roger Rousseau, Christophe Guilbaud, Isabelle Granger, Kamal Boubekeur, Patrick Batail, Enric Canadell, Pascale Auban-Senzier, Denis Jérôme

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An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, β″-(BEDT-TTF)4·(guest)n· [Re6Q6Cl8], (BEDT-TTF=bis-ethylene-dithiotetrathiafulvalene; Q = S, Se; guest = H2O, 1,4-dioxane, THF, CCl4, C2H5OH, CHCl3, CH2ClI, CH2ClBr, CH2Cl2, CH2OH-CH2OH, C5H5N, CH3COCH3, 2-hydroxy-tetrahydrofuran, CH3CN, CS2, C6H6), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H⋯Cl-μ-Re, (C-H)BEDT-TFF⋯Cl-μ-Re, C-H ⋯ Oguest, (C-H)guest ⋯ Cl-μ-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the π-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.

Original languageEnglish
Pages (from-to)3884-3900
Number of pages17
JournalChemistry - A European Journal
Issue number17
Publication statusPublished - Sep 2 2002



  • Cluster compounds
  • Hydrogen bonds
  • Metallic materials
  • Organic-inorganic interface
  • Radical ions

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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