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Intramolecular Dynamics of Asymmetric Lanthanide(III) Porphyrin Sandwich Complexes in Solution
Author(s) -
Babailov Sergey P.,
Coutsolelos Athanassios G.,
Dikiy Alexander,
Spyroulias Georgios A.
Publication year - 2001
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 - 10.1002/1099-0682(20011)2001:1<303::aid-ejic303>3.0.co;2-y
Subject(s) - chemistry , intramolecular force , porphyrin , lanthanide , tetraphenylporphyrin , crystallography , paramagnetism , ring (chemistry) , nuclear magnetic resonance spectroscopy , stereochemistry , computational chemistry , photochemistry , organic chemistry , ion , physics , quantum mechanics
Temperature dependencies of the 1 H NMR spectra of asymmetric double‐decker complexes of DyH(oep)(tpp) ( I ) and LuH(oep)(tpp) ( II ), where tpp is tetraphenylporphyrin and oep is octaethylporphyrin, have been analyzed. The kinetic and thermodynamic parameters for intramolecular phenyl ring rotations have been determined. The rotation in ( I ) is characterized by k (298 K) = 11.4 s −1 , Δ H ‡ = 48.0±6.0 kJ mol −1 , while in ( II ) the derived parameters are found to be k (298 K) = 14.0 s −1 , Δ H ‡ = 65.5±7.1 kJ mol −1 . The possible reasons for the different characteristics of these complexes are discussed. The structural parameters calculated for I and YbH(oep)(tpp) ( III ), indicate close similarities between the complexes. Nevertheless, it appears that the principal values of the molar paramagnetic susceptibility tensor (χ i ) differ significantly in these complexes.