Issue 10, 2015
From the journal:

Chemical Science

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

Wei Cao,a   Chen Gao,c   Yi-Quan Zhang,d   Dongdong Qi,a   Tao Liu,*b   Kang Wang,a   Chunying Duan,b   Song Gao*c  and  Jianzhuang Jiang*a  

* Corresponding authors

a Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing, China
E-mail: jianzhuang@ustb.edu.cn
Fax: +86-10-6233-2592

b State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China
E-mail: liutao@dlut.edu.cn

c Beijing National Laboratory of Molecular Science State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, China
E-mail: gaosong@pku.edu.cn

d Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing 210023, China

Abstract

With the coordination geometry of DyIII being relatively fixed, oxygen and sulfur atoms were used to replace one porphyrin pyrrole nitrogen atom of sandwich complex [(Bu)4N][DyIII(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 DyIII(Pc)(STBPP) > DyIII(Pc)(OTBPP) > [(Bu)4N][DyIII(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.

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

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Article information

DOI
https://doi.org/10.1039/C5SC02314A
Article type
Edge Article
Submitted
26 Jun 2015
Accepted
20 Jul 2015
First published
20 Jul 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2015,6, 5947-5954

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

W. Cao, C. Gao, Y. Zhang, D. Qi, T. Liu, K. Wang, C. Duan, S. Gao and J. Jiang, Chem. Sci., 2015, 6, 5947 DOI: 10.1039/C5SC02314A

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