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Single Crystalline Commensurate Metallic Assemblages of π-slabs and CdI2-Type Layers: Synthesis and Properties of β-(EDT-TTF-I2)2[Pb5/61/6I2]3 and β-(EDT-TTF-I2)2[Pb2/3+xAg1/3-2xxI2]3, x = 0.05
journal contribution
posted on 2003-02-14, 00:00 authored by Thomas Devic, Michel Evain, Yves Moëlo, Enric Canadell, Pascale Auban-Senzier, Marc Fourmigué, Patrick BatailThe ability of I···I van der Waals interactions to direct the self-assembly of slabs of the radical
cation of ethylenedithio-1,2-diiodo-tetrathiafulvalene, EDT-TTF-I2, and polymeric lead iodide covalent anionic
layers is demonstrated by the synthesis of single crystals of β-(EDT-TTF-I2)2•+[(Pb5/6□1/6I2)1/3-]3, triclinic,
P-1, a = 7.7818(8), b = 7.9760(8), c = 19.9668(2) Å, α = 82.409(12), β = 85.964(12), γ = 61.621(11)°,
V = 1080.76(19) Å3, R1, wR2 = 0.0459, 0.0947; and β-(EDT-TTF-I2)2•+[(Pb2/3+xAg1/3-2x□x I2)1/3-]3, x ≈ 0.05,
triclinic, P-1, a = 7.7744(8), b = 7.9193(8), c = 19.834(2) Å, α = 87.189(12), β = 83.534(12), γ =
61.602(11)°, V = 1067.4(2) Å3, R1, wR2 = 0.0508, 0.0997. The state-of-the-art, combined microprobe
and structural analysis of the metal site vacancies and occupancies patterns reveal a commensurate
organic−inorganic interface and point out the importance of halogen···halogen van der Waals interactions
to future studies aiming at directing interface topologies. The electronic structure, room-temperature metallic
character and metal−insulator transition at ca. 70 K of the two-dimensional organic slabs are retained
upon alloying of the inorganic sublattice with monocations. The room-temperature conductivity of the metallic
lead−silver alloy is 2 orders of magnitude larger than that of β-(EDT-TTF-I2)2•+[(Pb5/6□1/6I2)1/3-]3. This calls
for the study of materials with diverse alloying patterns with metal cations of different nature and charge.