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Indexed by:期刊论文

Date of Publication:2015-10-01

Journal:CHEMICAL SCIENCE

Included Journals:SCIE、EI、PubMed、Scopus

Volume:6

Issue:10

Page Number:5947-5954

ISSN No.:2041-6520

Abstract:With the coordination geometry of Dy-III being relatively fixed, oxygen and sulfur atoms were used to replace one porphyrin pyrrole nitrogen atom of sandwich complex [(Bu)(4)N][Dy-III(Pc)(TBPP)] [Pc = dianion of phthalocyanine, TBPP = 5,10,15,20-tetrakis[(4-tert-butyl) phenyl] porphyrin]. The energy barrier of the compounds was enhanced three times, with the order of Dy-III(Pc)(STBPP) > Dy-III(Pc)(OTBPP) > [(Bu)(4)N][Dy-III(Pc)(TBPP)] [STBPP = monoanion of 5,10,15,20-(4-tert-butyl) phenyl-21-thiaporphyrin, OTBPP = monoanion of 5,10,15,20-(4-tert-butyl)phenyl-21-oxaporphyrin]. Theoretical calculations offer reasonable explanations of such a significant enhancement. The energy barrier of 194 K for DyIII(Pc)(STBPP) represents the highest one among all the bis(tetrapyrrole) dysprosium SMMs, providing a strategy to rationally enhance the anisotropy and energy barrier via atom replacement.