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Guest-anion-induced rotation-restricted emission in UiO-66-NH2 and advanced structure elucidation

DOI: 10.1021/acs.chemmater.1c01674 DOI Help

Authors: Qi Xue (The Hong Kong Polytechnic University Shenzhen Research Institute; The Hong Kong Polytechnic University) , Ka Hin Chan (The Hong Kong Polytechnic University Shenzhen Research Institute; The Hong Kong Polytechnic University) , Cheuk Ki Yim (The Hong Kong Polytechnic University) , Bryan Kit Yue Ng (University of Oxford) , Tianxiang Chen (The Hong Kong Polytechnic University) , Sarah J. Day (Diamond Light Source) , Chiu Tang (Diamond Light Source) , Shogo Kawaguchi (Japan Synchrotron Radiation Research Institute) , Kwok-Yin Wong (The Hong Kong Polytechnic University) , Tsz Woon Benedict Lo (The Hong Kong Polytechnic University Shenzhen Research Institute; The Hong Kong Polytechnic University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: July 2021

Abstract: We report the guest-anion-induced photoluminescence enhancement of metal–organic frameworks (UiO-66-NH2), first based upon diffraction and computational evidence. We found that only limited anions, namely, carbonate and fluoride, can lead to a significant enhancement in photoluminescence, whereas their related anions, such as acetate and chloride, cannot. The optimized crystal structures reveal that the guest carbonate and fluoride ions interact with four framework amino functional groups through hydrogen bonding (ca. 1.6–1.7 Å) that ultimately forms a quaternary (−N(H))4···X– molecular bridge around the nodal center. Hence, the hydrogen-bonded molecular bridge not only restricts the intermolecular C–C rotation of the linker molecules but also greatly perturbs the electronic densities between the guest anions and the framework amino groups.

Journal Keywords: Charge transfer; Anions; Crystal structure; Metal organic frameworks; Diffraction

Subject Areas: Materials, Chemistry

Facility: BL02B2 at SPring-8

Added On: 05/07/2021 08:49

Discipline Tags:

Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags: