Sequential Transformation of Zirconium(IV)-MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers

Shuai Yuan; Jun-Sheng Qin; Jian Su; Bao Li; Jialuo Li; Wenmiao Chen; Hannah F Drake; Peng Zhang; Daqiang Yuan; Jinglin Zuo; Hong-Cai Zhou

doi:10.1002/anie.201808568

Sequential Transformation of Zirconium(IV)-MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers

Angew Chem Int Ed Engl. 2018 Sep 17;57(38):12578-12583. doi: 10.1002/anie.201808568. Epub 2018 Aug 27.

Authors

Shuai Yuan¹, Jun-Sheng Qin¹, Jian Su², Bao Li¹, Jialuo Li¹, Wenmiao Chen¹, Hannah F Drake¹, Peng Zhang¹, Daqiang Yuan³, Jinglin Zuo², Hong-Cai Zhou^{1

4}

Affiliations

¹ Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
² State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, P. R. China.
³ State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
⁴ Department of Materials Science and Engineering, Texas A&M University, College Station, TX, 77840, USA.

PMID: 30102004
DOI: 10.1002/anie.201808568

Abstract

Heterometallic metal-organic frameworks (MOFs) allow the precise placement of various metals at atomic precision within a porous framework. This new level of control by MOFs promises fascinating advances in basic science and application. However, the rational design and synthesis of heterometallic MOFs remains a challenge due to the complexity of the heterometallic systems. Herein, we show that bimetallic MOFs with MX₂ (INA)₄ moieties (INA=isonicotinate; M=Co²⁺ or Fe²⁺ ; X=OH^- , Cl^- , Br^- , I^- , NCS^- , or NCSe^- ) can be generated by the sequential modification of a Zr-based MOF. This multi-step modification not only replaced the linear organic linker with a square planar MX₂ (INA)₄ unit, but also altered the symmetry, unit cell, and topology of the parent structure. Single-crystal to single-crystal transformation is realized so that snapshots for transition process were captured by successive single-crystal X-ray diffraction. Furthermore, the installation of Co(NCS)₂ (INA)₄ endows field-induced slow magnetic relaxation property to the diamagnetic Zr-MOF.

Keywords: heterometallic MOFs; metal-organic frameworks; postsynthetic modification; single-crystal to single-crystal transformation.

Abstract

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