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Article
Light-Induced Photochemical Changes in Copper(I) Thiocyanate Complexes Decorated with Halopyridines. Optical Memory Manifestation
JOURNAL OF PHYSICAL CHEMISTRY C
  • Aaron Nicholas, University of Maine
  • Brooke M Otten, University of North Texas
  • Gerardo Ayala, College of William and Mary
  • James Hutchinson, University of Maine
  • Lukasz Wojtas, University of South Florida
  • Mohammad A Omary, University of North Texas
  • Robert D Pike, College of William and Mary
  • Howard H Patterson, University of Maine
Document Type
Article
Publication Date
10-17-2017
Disciplines
Abstract

We report on the photoluminescence of {CuSCN(3-XPy) 2 } n crystals (X = Br, Cl; Py = pyridine). Laser excitation at 266 nm for CuSCN(3-BrPy) 2 at 78 K results in a decrease in the luminescence intensity with increasing irradiation time. Heating the sample to 298 K and re- cooling to 78 K results in recovery of the original luminescence intensity, hence manifesting an optical memory effect. Laser irradiation at longer or shorter wavelengths fails to produce a reduction in emission intensity. Interestingly, CuSCN(3-ClPy) 2 , despite being isomorphic, does not undergo emission intensity changes regardless of laser irradiation wavelength variation. Density Functional Theory (DFT) and Time Dependent DFT (TD-DFT) calculations were performed on an adjacent chain model to explore the photochemical change that occurs upon laser irradiation. The observed reduction in luminescence intensity is attributed to photo-induced electron transfer quenching in which Cu(I) is oxidized to a non-luminescent Cu(II) with capture of the halogen by a neighboring SCN ligand on the adjacent coordination polymer chain.

DOI
10.1021/acs.jpcc.7b06871
Comments

This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in the Journal of Physical Chemistry C, copyright © American Chemical Society after peer review. To access the final edited and published work see 10.1021/acs.jpcc.7b06871.

Journal Article URL
https://pubs.acs.org/doi/10.1021/acs.jpcc.7b06871
Publisher Statement

This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in the Journal of Physical Chemistry C, copyright © American Chemical Society after peer review. To access the final edited and published work see 10.1021/acs.jpcc.7b06871.

Citation Information
Aaron Nicholas, Brooke M Otten, Gerardo Ayala, James Hutchinson, et al.. "Light-Induced Photochemical Changes in Copper(I) Thiocyanate Complexes Decorated with Halopyridines. Optical Memory Manifestation" JOURNAL OF PHYSICAL CHEMISTRY C Vol. 121 Iss. 45 (2017) p. 25430 - 25439
Available at: http://works.bepress.com/robert-pike/118/