Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks

Xin Zheng, Rosmi Reji, Matthew C. Drummer, Haiying He, Jens Niklas, Nicholas P. Weingartz, Igor L. Bolotin, Lin X. Chen, Oleg G. Poluektov, Peter Zapol, Ksenija D. Glusac*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical gaps. Here, we demonstrate a facile approach to optical gap tuning via postsynthetic modifications of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl3 was shown to induce three different chemical reactions: oxidative dehydrogenation, chlorination, and one-electron oxidation of the ligands. The result of these reactions was a gradual decrease in the optical gap from 2.95 eV to as little as 0.69 eV. Steady-state and time-resolved optical spectroscopy, mass spectrometry, and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations, provide insights into the chemical transformations that affect the optical properties of the MOF. The facile optical gap tuning reported here has promising application in the utilization of photoresponsive MOFs in photocatalysis, sensing, and other light-triggered applications.

Original languageEnglish (US)
Pages (from-to)1643-1650
Number of pages8
JournalACS Applied Optical Materials
Volume1
Issue number10
DOIs
StatePublished - Oct 27 2023

Keywords

  • optical gap tuning
  • postsynthetic modification
  • stable aromatic radical cation
  • transient absorption spectroscopy
  • zirconium metal-organic frameworks

ASJC Scopus subject areas

  • Spectroscopy
  • Electronic, Optical and Magnetic Materials
  • Atomic and Molecular Physics, and Optics

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