Heterometallic Multinuclear Nodes Directing MOF Electronic Behavior

Author(s)

Otega A. Ejegbavwo
Anna A. Berseneva
Corey R. Martin
Gabrielle A. Leith
Shubham Pandey
Amy J. Brandt
Kyoung Chul Park
Abhijai Mathur
Sharfa Farzandh
Vladislav V. Klepov
Brittany J. Heiser
Mvs Chandrashekhar
Stavros G. Karakalos
Mark D. Smith
Simon R. Phillpot
Sophya Garashchuk
Donna A. Chen
Natalia B. Shustova Prof. Dr., University of South CarolinaFollow

Document Type

Article

Abstract

Metal node engineering in combination with modularity, topological diversity, and porosity of metal–organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal−property trends, i.e., connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectance spectroscopies, and density functional theory calculations. The results of Bader charge analysis and studies employing the Voronoi–Dirichlet partition of crystal structures are also presented. As an example of frameworks with different nodal arrangements, we have chosen MOFs with mononuclear, binuclear, and pentanuclear nodes, primarily consisting of first-row transition metals, that are incorporated in HHTP-, BTC-, and NIP-systems, respectively (HHTP³− = triphenylene-2,3,6,7,10,11-hexaone; BTC³− = 1,3,5-benzenetricarboxylate; and NIP²− = 5-nitroisophthalate). Through probing framework electronic profiles, we demonstrate structure–property relationships, and also highlight the necessity for both comprehensive analysis of trends in metal properties, and novel avenues for preparation of heterometallic multinuclear isoreticular structures, which are critical components for on-demand tailoring of properties in heterometallic systems.

Digital Object Identifier (DOI)

https://doi.org/10.1039/D0SC03053H

Publication Info

Published in Chemical Science, Volume 11, Issue 28, 2020, pages 7379-7389.

Rights

© The Royal Society of Chemistry 2020 This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

APA Citation

Ejegbavwo, O. A., Berseneva, A. A., Martin, C. R., Leith, G. A., Pandey, S., Brandt, A. J., Park, K. C., Mathur, A., Farzandh, S., Klepov, V. V., Heiser, B. J., Chandrashekhar, M., Karakalos, S. G., Smith, M. D., Phillpot, S. R., Garashchuk, S., Chen, D. A., & Shustova, N. B. (2020). Heterometallic multinuclear nodes directing MOF electronic behavior. Chemical Science, 11(28), 7379–7389. https://doi.org/10.1039/d0sc03053h