Release Time:2019-03-09  Hits:

Indexed by: Journal Article

Date of Publication: 2015-10-01

Journal: CHEMICAL SCIENCE

Included Journals: Scopus、PubMed、EI、SCIE

Volume: 6

Issue: 10

Page Number: 5947-5954

ISSN: 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.