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Multicomponent Ionic Complexes of Cobalt( II ) Tetraphenylporphyrin with C 60 Fullerides − Transition from the σ‐Bonded [(Co II TPP)·(C 60 − )] Anion to Nonbonded Co II TPP and C 60 ·− Components
Author(s) -
Konarev Dmitri V.,
Neretin Ivan S.,
Saito Gunzi,
Slovokhotov Yury L.,
Otsuka Akihiro,
Lyubovskaya Rimma N.
Publication year - 2004
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.200300874
Subject(s) - chemistry , tetramethylammonium , electron paramagnetic resonance , crystallography , ionic bonding , tetraphenylporphyrin , cobalt , molecule , crystal structure , ion , polyoxometalate , x ray crystallography , inorganic chemistry , stereochemistry , catalysis , photochemistry , porphyrin , diffraction , organic chemistry , physics , nuclear magnetic resonance , optics
New multicomponent ionic complexes containing [(Cation + )·(C 60 − )] fullerides and neutral Co II TPP molecules were obtained [the cations are Cs + ( 1 ), tetramethylammonium (CH 3 ) 4 N + ( 2 ) and N ‐methylpyridinium N ‐MePy + ( 3 )]. The crystal structure of 1 determined from single‐crystal X‐ray diffraction analysis contains chains of alternating Co II TPP and C 60 ·− units with voids accommodating solvated [(Cs + )·(C 6 H 5 CN) 1.64 ]·CH 3 CN counter cations. Relatively long Co ··· C distances between Co II TPP and C 60 ·− in 1 (2.55−3.05 Å) indicate the absence of noticeable bonding of Co II TPP and C 60 ·− . This is consistent with the EPR spectrum of 1 , which manifests two EPR signals with g = 2.0009 and 2.4982 attributable to C 60 ·− and Co II TPP, respectively. In contrast to 1 , complexes 2 and 3 contain EPR‐silent, σ‐bonded [(Co II TPP)·(C 60 − )] anions. The influence of the size of counter cations on the stability of σ‐bonded [(Co II TPP)·(C 60 − )] anions in ionic [(Cation + )·(Co II TPP)·(C 60 − )] complexes is analyzed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)