Single Crystalline Commensurate Metallic Assemblages of π-slabs and CdI₂-Type Layers: Synthesis and Properties of β-(EDT-TTF-I₂)₂[Pb_5/6_1/6I₂]₃ and β-(EDT-TTF-I₂)₂[Pb_2/3+<i>_x</i>Ag_1/3-2<i>_x</i><i>_x</i>I₂]₃, <i>x</i> = 0.05

Abstract

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-I(2), and polymeric lead iodide covalent anionic layers is demonstrated by the synthesis of single crystals of beta-(EDT-TTF-I(2))(2)(.+)[(Pb(5/6) square (1/6)I(2))(1/3-)](3), triclinic, P-1, a = 7.7818(8), b = 7.9760(8), c = 19.9668(2) A, alpha = 82.409(12), beta = 85.964(12), gamma = 61.621(11) degrees, V = 1080.76(19) A(3), R1, wR2 = 0.0459, 0.0947; and beta-(EDT-TTF-I(2))(2)(.+)[(Pb(2/3+x)Ag(1/3-2x)square(x)I(2))(1/3-)](3), x approximately 0.05, triclinic, P-1, a = 7.7744(8), b = 7.9193(8), c = 19.834(2) A, alpha = 87.189(12), beta = 83.534(12), gamma = 61.602(11) degrees, V = 1067.4(2) A(3), 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 beta-(EDT-TTF-I(2))(2)(.+)[(Pb(5/6) square (1/6)I(2))(1/3-)](3). This calls for the study of materials with diverse alloying patterns with metal cations of different nature and charge.