TY - JOUR
T1 - Direct Identification of Mixed-Metal Centers in Metal-Organic Frameworks
T2 - Cu3(BTC)2Transmetalated with Rh2+Ions
AU - Metavarayuth, Kamolrat
AU - Ejegbavwo, Otega
AU - McCarver, Gavin
AU - Myrick, Michael L.
AU - Makris, Thomas M.
AU - Vogiatzis, Konstantinos D.
AU - Senanayake, Sanjaya D.
AU - Manley, Olivia M.
AU - Ebrahim, Amani M.
AU - Frenkel, Anatoly I.
AU - Hwang, Sooyeon
AU - Rajeshkumar, Thayalan
AU - Jimenez, Juan D.
AU - Chen, Kexun
AU - Shustova, Natalia B.
AU - Chen, Donna A.
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/10/1
Y1 - 2020/10/1
N2 - 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 (BTC3- = 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 (CuxRh1-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 (CuxRh1-x)3(BTC)2 on the nanoscale.
AB - 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 (BTC3- = 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 (CuxRh1-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 (CuxRh1-x)3(BTC)2 on the nanoscale.
UR - https://www.scopus.com/pages/publications/85092682422
U2 - 10.1021/acs.jpclett.0c02539
DO - 10.1021/acs.jpclett.0c02539
M3 - Article
C2 - 32894952
AN - SCOPUS:85092682422
SN - 1948-7185
VL - 11
SP - 8138
EP - 8144
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 19
ER -