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Tuning the negative thermal expansion behavior of the metal–organic framework Cu3BTC2 by retrofitting

DOI: 10.1021/jacs.9b04755 DOI Help

Authors: Christian Schneider (Technical University of Munich) , David Bodesheim (Technical University of Munich) , Michael G. Ehrenreich (Technical University of Munich) , Valentina Crocellà (University of Turin) , János Mink (Hungarian Academy of Sciences; University of Pannonia) , Roland A. Fischer (Technical University Munich) , Keith T. Butler (Scientific Computing Department, Rutherford Appleton Laboratory) , Gregor Kieslich (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: June 2019
Diamond Proposal Number(s): 17914

Abstract: The modular building principle of metal–organic frameworks (MOFs) presents an excellent platform to explore and establish structure–property relations that tie microscopic to macroscopic properties. Negative thermal expansion (NTE) is a common phenomenon in MOFs and is often ascribed to collective motions that can move through the structure at sufficiently low energies. Here, we show that the introduction of additional linkages in a parent framework, retrofitting, is an effective approach to access lattice dynamics experimentally, in turn providing researchers with a tool to alter the NTE behavior in MOFs. By introducing TCNQ (7,7,8,8-tetracyanoquinodimethane) into the prototypical MOF Cu3BTC2 (BTC = 1,3,5-benzenetricarboxylate; HKUST-1), NTE can be tuned between αV = −15.3 × 10–6 K–1 (Cu3BTC2) and αV = −8.4 × 10–6 K–1 (1.0TCNQ@Cu3BTC2). We ascribe this phenomenon to a general stiffening of the framework as a function of TCNQ loading due to additional network connectivity, which is confirmed by computational modeling and far-infrared spectroscopy. Our findings imply that retrofitting is generally applicable to MOFs with open metal sites, opening yet another way to fine-tune properties in this versatile class of materials.

Subject Areas: Chemistry, Materials


Instruments: I11-High Resolution Powder Diffraction