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Tetrathiafulvalene Dimer Merged with a Binuclear Ring of Sn and Sb: Synthesis and Molecular Structures Induced by Heteroatoms
Author(s) -
Hasegawa Masashi,
Shirai Masaki,
Mazaki Yasuhiro
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800571
Subject(s) - chemistry , tetrathiafulvalene , crystallography , supramolecular chemistry , moiety , conformational isomerism , dimer , cyclic voltammetry , ring (chemistry) , heteroatom , crystal structure , stereochemistry , molecule , electrochemistry , organic chemistry , electrode
In this study, we describe the synthesis and characterization of dimeric tetrathiafulvalene (TTF) derivatives that are doubly bridged by Sn ( 1 ) and Sb ( 2a ) atoms as a new class of organic‐inorganic hybrid compounds able to provide enhanced dimensionality in the solid state. The antimony heterocyclic framework was constructed by a simple Sn–Sb metal exchange reaction of a 1,4‐distannine moiety with p ‐tolyl antimony dichloride ( p ‐tolSbCl 2 ). Compound 2a was obtained in cis and trans forms as a stable configurational isomer. From X‐ray crystallographic analysis, there were three conformational isomers in which the tolyl rings were directed in the endo or exo direction. Crystal packing revealed a supramolecular three‐dimensional network through intermolecular short contacts of Sb ··· S and Sb ··· π. These packing forces gave a trans ‐ 2a exo–exo conformation in the crystal, although the theoretical calculations predict its instability compared with other conformers. Cyclic voltammetry (CV) measurements of 1 and cis/trans ‐ 2a revealed two pairs of reversible redox processes corresponding to the formation of TTF/TTF · + and TTF · + /TTF 2+ . Furthermore, CV of cis/trans ‐ 2a also revealed the reduction waves derived from the reduction of Sb III . Dicationic and tetracationic species were prepared by chemical oxidation, and their electronic structures were also investigated by electronic spectroscopy.