Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions

Metavarayuth, Kamolrat; Ejegbavwo, Otega; McCarver, Gavin; Myrick, Michael L.; Makris, Thomas M.; Vogiatzis, Konstantinos D.; Manley, Olivia M.; Senanayake, Sanjaya D.; Ebrahim, Amani M.; Frenkel, Anatoly I.; Hwang, Sooyeon; Rajeshkumar, Thayalan; Jimenez, Juan D.; Chen, Kexun; Shustova, Natalia B.; Chen, Donna A.

doi:10.1021/acs.jpclett.0c02539

Title: Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu₃(BTC)₂ Transmetalated with Rh²⁺ Ions

Journal Article · Mon Sep 07 00:00:00 EDT 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c02539· OSTI ID:1716757

Metavarayuth, Kamolrat ^[1]; Ejegbavwo, Otega ^[1]; McCarver, Gavin ^[2]; Myrick, Michael L. ^[1]; Makris, Thomas M. ^[1]; Vogiatzis, Konstantinos D. ^[2]; Manley, Olivia M. ^[1];

^[3]; Ebrahim, Amani M. ^[4]; Frenkel, Anatoly I. ^[5]; Hwang, Sooyeon ^[6]; Rajeshkumar, Thayalan ^[2]; Jimenez, Juan D. ^[1]; Chen, Kexun ^[1]; Shustova, Natalia B. ^[1]; Chen, Donna A. ^[1]

Univ. of South Carolina, Columbia, SC (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Raman spectroscopy was used to establish direct evidence of heterometallic metal centers in a metal–organic framework (MOF). The Cu₃(BTC)₂ MOF HKUST-1 (BTC^3– = benzenetricarboxylate) was transmetalated by heating it in a solution of RhCl₃ to substitute Rh²⁺ ions for Cu²⁺ ions in the dinuclear paddlewheel nodes of the framework. In addition to the Cu–Cu and Rh–Rh stretching modes, Raman spectra of (Cu_xRh_1–x)₃(BTC)₂ show the Cu–Rh stretching mode, indicating that mixed-metal Cu–Rh nodes are formed after transmetalation. Density functional theory studies confirmed the assignment of a Raman peak at 285 cm^–1 to the Cu–Rh stretching vibration. Electron paramagnetic resonance spectroscopy experiments further supported the conclusion that Rh²⁺ ions are substituted into the paddlewheel nodes of Cu₃(BTC)₂ to form an isostructural heterometallic MOF, and electron microscopy studies showed that Rh and Cu are homogeneously distributed in (Cu_xRh_1–x)₃(BTC)₂ on the nanoscale.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0019360; SC0001004

OSTI ID:: 1716757

Report Number(s):: BNL-220600-2020-JAAM

Journal Information:: Journal of Physical Chemistry Letters, Vol. 11, Issue 19; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions

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Title: Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu₃(BTC)₂ Transmetalated with Rh²⁺ Ions