Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets

Su, Jian; Yuan, Shuai; Li, Jing; Wang, Hai‐Ying; Ge, Jing‐Yuan; Drake, Hannah F.; Leong, Chanel F.; Yu, Fei; D'Alessandro, Deanna M.; Kurmoo, Mohamedally; Zuo, Jing‐Lin; Zhou, Hong‐Cai

doi:10.1002/chem.202004883

Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets

Journal Article · Thu Dec 03 00:00:00 EST 2020 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202004883· OSTI ID:1786135

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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
Department of Chemistry Texas A&,M University College Station TX 77843 USA
School of Chemistry The University of Sydney Sydney, New South Wales 2006 Australia
Institut de Chimie de Strasbourg, CNRS-UMR7177 Université de Strasbourg 4 rue Blaise Pascal Strasbourg 67000 France

Abstract

Using the redox‐active tetrathiafulvalene tetrabenzoate (TTFTB ⁴⁻ ) as the linker, a series of stable and porous rare‐earth metal–organic frameworks (RE‐MOFs), [RE ₉ (μ ₃ ‐OH) ₁₃ (μ ₃ ‐O)(H ₂ O) ₉ (TTFTB) ₃ ] ( 1‐RE , where RE=Y, Sm, Gd, Tb, Dy, Ho, and Er) were constructed. The RE ₉ (μ ₃ ‐OH) ₁₃ (μ ₃ ‐O) (H ₂ O) ₉ ](CO ₂ ) ₁₂ clusters within 1‐RE act as segregated single‐molecule magnets (SMMs) displaying slow relaxation. Interestingly, upon oxidation by I ₂ , the S= 0 TTFTB ⁴⁻ linkers of 1‐RE were converted into S = TTFTB ^.3− radical linkers which introduced exchange‐coupling between SMMs and modulated the relaxation. Furthermore, the SMM property can be restored by reduction in N,N ‐dimethylformamide. These results highlight the advantage of MOFs in the construction of redox‐switchable SMMs.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001015

OSTI ID:: 1786135

Alternate ID(s):: OSTI ID: 1850686

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 2 Vol. 27; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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