NMR investigation of intramolecular dynamics of heteroleptic triple-decker (porphyrinato)(phthalocyaninato) lanthanides |
| |
Authors: | Birin Kirill P Gorbunova Yulia G Tsivadze Aslan Yu |
| |
Institution: | A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky pr., 31, 119991, Moscow, Russia. kirill.birin@gmail.com |
| |
Abstract: | Intramolecular dynamics of meso-aryl substituents of porphyrin deck in the triple-decker lanthanide (porphyrinato)(phthalocyaninates) of symmetrical type Br(4)TPP]Ln(15C5)(4)Pc]LnBr(4)TPP] (Ln = La, Nd, Eu; Br(4)TPP] = tetrakis-5,10,15,20-(4-bromophenyl)-porphyrinato-ligand; (15C5)(4)Pc] = tetrakis-(15-crown-5)-phthalocyaninato-ligand) are investigated. Attempts to achieve coalescence were not successful, although the trend of exchanging protons to coalescence point was observed in the case of Nd and Eu complexes. The analysis of NOESY cross-peaks between exchanging protons allowed to evaluate the rotation rate constants at different temperatures. The activation barrier of the meso-aryl substituent rotation was calculated with Arrhenius equation based on determined rate constants. The rate constants are lower and activation barriers are higher than ones found previously for related compounds. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|