Rational enhancement of the energy barrier of bis(tetrapyrrole) dysprosium SMMs via replacing atom of porphyrin core

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 Dy(III)(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.