A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor–Acceptor Fulleretic Covalent-Organic Materials

Gabrielle A. Leith, Allison M. Rice, Brandon J. Yarbrough, Anna A. Berseneva, Richard T. Ly, Charles N. Buck, Denis Chusov, Amy J. Brandt, Donna A. Chen, Benjamin W. Lamm, Morgan Stefik, Kenneth S. Stephenson, Mark D. Smith, Aaron K. Vannucci, Perry J. Pellechia, Sophya Garashchuk, Natalia B. Shustova

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.

Original languageEnglish
Pages (from-to)6000-6006
Number of pages7
JournalAngewandte Chemie - International Edition
Volume59
Issue number15
DOIs
StatePublished - Apr 6 2020
Externally publishedYes

Funding

This work was supported by the NSF CAREER Award (DMR‐1553634). N.B.S thanks the Cottrell Scholar Award from the Research Corporation for Science Advancement, Sloan Research Fellowship provided by Alfred P. Sloan Foundation, and Camille Dreyfus Teaching‐Scholar Award provided by Henry and Camille Dreyfus Foundation. This material is based upon work partially supported by the National Science Foundation under Grant CHE‐1565985, and in part by the National Science Foundation EPSCoR Program under NSF Award OIA‐1655740. M.S. and B.W.L. acknowledge support of National Science Foundation under NSF Award DMR‐1752615. This work made use of the South Carolina SAXS Collaborative. We also acknowledge USC's XPS user facility, as well as Dr. Stavros Karakalos for his help at the facility. Computations were performed on an HPC cluster funded by the National Science Foundation under Grant No. CHE‐1048629.

Keywords

  • covalent-organic frameworks
  • donor–acceptor interactions
  • electronic structure
  • fulleretic materials
  • redox-activity

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