A Record-Breaking Loading Capacity for Single-Molecule

Jun 11, 2019 - A Record-Breaking Loading Capacity for Single-Molecule Magnet Mn12 Clusters Achieved in a Mesoporous Ln-MOF ... Subscribed Access ...
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Letter Cite This: ACS Appl. Electron. Mater. 2019, 1, 804−809

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A Record-Breaking Loading Capacity for Single-Molecule Magnet Mn12 Clusters Achieved in a Mesoporous Ln-MOF Hui-Jun Chen,† Xiu-Ying Zheng,† Ya-Rui Zhao,† Da-Qiang Yuan,*,‡ Xiang-Jian Kong,† La-Sheng Long,*,† and Lan-Sun Zheng† †

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Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China ‡ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China S Supporting Information *

ABSTRACT: A chiral mesoporous lanthanide-based metal−organic framework (Ln-MOF) was synthesized. More importantly, its loading capacity for Mn12Ac reached 40.15 mol %, which is not only larger than that reported for porous materials to date thus far but also significantly larger than that observed on the surface of LB film. Investigations on the crystal structures and the nitrogen adsorption isotherms reveal that the well-matched porous size with that of SMMs in MOFs, the flexible porosity of the MOFs, and the interactions between MOFs and SMMs are key for enhancing the loading capacity for SMMs in the MOFs. KEYWORDS: lanthanide-based mesoporous metal−organic frameworks, single-molecule magnets (SMMs), loading capacity, flexibility, hydrogen-bonding interactions

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the long-range order of SMMs.11−13 However, because the encapsulation of the SMMs into the pores of MOFs not only requires their pore size to match the size of the SMMs well but also requires an appropriate interaction between the SMMs and the pores of the MOFs, only three examples of this approach have been reported to date.11−13 Moreover, in two of these studies, the loading capacity for the SMMs was quite limited (