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A Radical‐Radical and Metal–Metal Coupling Tetrathiafulvalene Derivative in which Organic Radicals Directly Coordinate to Cu II Ions
Author(s) -
Lu Wen,
Zhang Yong,
Dai Jie,
Zhu QinYu,
Bian GuoQing,
Zhang DeQing
Publication year - 2006
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.200500945
Subject(s) - chemistry , tetrathiafulvalene , radical , stacking , metal , crystallography , amide , metal ions in aqueous solution , crystal structure , ionic bonding , copper , derivative (finance) , inorganic chemistry , ion , photochemistry , molecule , organic chemistry , financial economics , economics
A new dinuclear metal complex including tetrathiafulvalene (TTF) radicals as ligands has been prepared and characterized, [{DMT‐TTF(CONH 2 ) 2 } 2 Cu 2 Cl 6 ] ( 1 ), DMT‐TTF(CONH 2 ) 2 = o ‐bis(amido)‐appended dimethylthio‐tetrathiafulvalene. The compound is an uncommon example in which TTF radicals directly coordinate to the copper( II ) halide by the amido group. Crystal structure analysis shows that it is a unique coordination bond/H‐bond/S ··· S stacking cooperative system with two radicals and two paramagnetic transition metal ions, TTF + · –Cu II –Cu II –TTF + · . In the structure of 1 , the DMT‐TTF units form dimers with very strong S ··· S interactions. The Cu II –O(amide) distance of the coordination bond is 2.271(2) Å and the S ··· S stacking distances between the radicals are in the range 3.345–3.489 Å. The metal–metal ions are mildly antiferromagnetically coupled (2 J 1 =–58.4 cm –1 ), while the radical pairs are strongly antiferromagnetically coupled (2 J 2 > –1000 cm –1 ).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)