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Single Crystalline Commensurate Metallic Assemblages of π-slabs and CdI 2 -Type Layers: Synthesis and Properties of β-(EDT-TTF-I 2 ) 2 [Pb 5/6 1/6 I 2 ] 3 and β-(EDT-TTF-I 2 ) 2 [Pb 2/3+ x Ag 1/3-2 x x I 2 ] 3 , x = 0.05

2003; American Chemical Society; Volume: 125; Issue: 11 Linguagem: Inglês

10.1021/ja0290431

1943-2984

Thomas Devic, M. Evain, Yves Moëlo, Enric Cañadell, Pascale Auban‐Senzier, Marc Fourmigué, Patrick Batail,

Perovskite Materials and Applications

The 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.