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New Organic Metals Based on BDH‐TTP Radical Cation Salts with the Photochromic Nitroprusside Anion [FeNO(CN) 5 ] 2–
Author(s) -
Shevyakova I.,
Buravov L.,
Tkacheva V.,
Zorina L.,
Khasanov S.,
Simonov S.,
Yamada J.,
Canadell E.,
Shibaeva R.,
Yagubskii E.
Publication year - 2004
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200305170
Subject(s) - triclinic crystal system , crystal structure , radical ion , crystallography , monoclinic crystal system , molecule , nitrobenzene , ion , materials science , chemistry , stereochemistry , organic chemistry , catalysis
Three new 2,5‐bis(1,3‐dithiolan‐2‐ylidene)‐1,3,4,6‐tetrathiapentalene (BDH‐TTP) radical cation salts with the photochromic nitroprusside anion have been synthesized: κ‐(BDH‐TTP) 4 [FeNO(CN) 5 ]·NB ( 1 ), κ‐(BDH‐TTP) 4 [FeNO(CN) 5 ] ( 2 ), and (BDH‐TTP) 2 [FeNO(CN) 5 ] ( 3 ). The salts were characterized by single‐crystal X‐ray diffraction, electrical resistance measurements, and electronic band structure calculations. The crystals of 1 and 2 have a layered structure in which the BDH‐TTP layers of κ‐type alternate with anionic sheets. Solvent (nitrobenzene) molecules are also involved in the composition of the anion sheet of 1 . The crystals of 1 have triclinic symmetry and two crystallographically independent BDH‐TTP radical cations in the unit cell, while there is only one independent radical cation in the monoclinic structure of 2 . The salts 1 and 2 are stable quasi‐2D metals down to 4.2 K, while 3 , with full charge transfer, is a semiconductor with low conductivity at room temperature. It is suggested that the κ‐type layers of BDH‐TTP are more robust than those of BEDT‐TTF and its derivatives and the consequences for the electronic structure are discussed.