An Electrically Conductive Tetrathiafulvalene-Based Hydrogen-Bonded Organic Framework

Kent O. Kirlikovali, Subhadip Goswami, Mohammad Rasel Mian, Matthew D. Krzyaniak, Michael R. Wasielewski, Joseph T. Hupp, Peng Li, Omar K. Farha*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations

Abstract

Recent advancements in the development of conductive metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have sparked interest in a variety of applications that leverage electronic materials due to the inherent tunability, porosity, and crystallinity associated with these materials. Hydrogen-bonded organic frameworks (HOFs) comprise an emerging class of complementary porous materials that assemble crystalline networks mainly from intermolecular hydrogen-bonding interactions; however, relatively few reports on functional HOFs exist as these reversible interactions are much weaker than the coordination or covalent bonds found in the former frameworks, which presents additional challenges in the isolation and activation of HOFs. In this work, we introduce an approach to access a permanently porous HOF derived from a tetrathiafulvalene (TTF) core, which is the first HOF reported to date that exhibits electrical conductivity. Upon precipitation from solution, HOF-110 self-assembles in a preferred orientation that contains vertical columns of TTF dimers, and the postsynthetic incorporation of iodine within the nanoporous channels of this framework affords pressed pellet conductivity values of up to 6.0 × 10-7 S·cm-1, which is an almost 30-fold improvement compared with pressed pellets of the pristine framework. Extensive structural characterization studies suggest the presence of radical mixed-valence TTF/TTF·+ species within these materials, which is consistent with previous reports on analogous TTF-based MOFs and COFs. Overall, this work presents a viable strategy to develop robust, electrically conductive frameworks built from purely intermolecular interactions, further expanding the toolbox available for the assembly of functional porous materials.

Original languageEnglish (US)
Pages (from-to)128-135
Number of pages8
JournalACS Materials Letters
Volume4
Issue number1
DOIs
StatePublished - Jan 3 2022

Funding

O.K.F. and J.T.H. acknowledge support from the Defense Threat Reduction Agency under Award Number HDTRA1-19-1-0010. K.O.K. gratefully acknowledges support from the IIN Postdoctoral Fellowship and the Northwestern University International Institute for Nanotechnology. This work was supported by the National Science Foundation under Award DMR-2003739 (M.R.W.). This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). The authors thank Rebecca Sponenburg and the Northwestern University Quantitative Bioelement Imaging Center (QBIC) for performing ICP-OES and -MS measurements. The authors thank Dr. Timur Islamoglu for helpful discussions.

ASJC Scopus subject areas

  • General Chemical Engineering
  • Biomedical Engineering
  • General Materials Science

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