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Title: Evidence for Interfacial Halogen Bonding

Abstract

Abstract A homologous series of donor–π–acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye‐X (X=F, Cl, Br, and I) was immobilized on a TiO 2 surface to investigate how the halogen substituents affect the reaction between the light‐induced charge‐separated state, TiO 2 (e )/ Dye‐X + , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye‐F < Dye‐Cl < Dye‐Br < Dye‐I . Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ‐hole on the heavier halogens, the differences in dye regeneration kinetics for Dye‐Cl , Dye‐Br , and Dye‐I are ascribed to the extent of halogen bonding with the nucleophilic solution species.

Authors:
 [1];  [2];  [2];  [2];  [2];  [1];  [1];  [2]
  1. Department of Chemistry The University of North Carolina at Chapel Hill Murray Hall 2202B Chapel Hill NC 27599-3290 USA
  2. Departments of Chemistry and Chemical &, Biological Engineering The University of British Columbia 2036 Main Mall Vancouver BC V6T1Z1 Canada
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401853
Grant/Contract Number:  
SC0013461
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 128 Journal Issue: 20; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Swords, Wesley B., Simon, Sarah J. C., Parlane, Fraser G. L., Dean, Rebecca K., Kellett, Cameron W., Hu, Ke, Meyer, Gerald J., and Berlinguette, Curtis P. Evidence for Interfacial Halogen Bonding. Germany: N. p., 2016. Web. doi:10.1002/ange.201510641.
Swords, Wesley B., Simon, Sarah J. C., Parlane, Fraser G. L., Dean, Rebecca K., Kellett, Cameron W., Hu, Ke, Meyer, Gerald J., & Berlinguette, Curtis P. Evidence for Interfacial Halogen Bonding. Germany. https://doi.org/10.1002/ange.201510641
Swords, Wesley B., Simon, Sarah J. C., Parlane, Fraser G. L., Dean, Rebecca K., Kellett, Cameron W., Hu, Ke, Meyer, Gerald J., and Berlinguette, Curtis P. 2016. "Evidence for Interfacial Halogen Bonding". Germany. https://doi.org/10.1002/ange.201510641.
@article{osti_1401853,
title = {Evidence for Interfacial Halogen Bonding},
author = {Swords, Wesley B. and Simon, Sarah J. C. and Parlane, Fraser G. L. and Dean, Rebecca K. and Kellett, Cameron W. and Hu, Ke and Meyer, Gerald J. and Berlinguette, Curtis P.},
abstractNote = {Abstract A homologous series of donor–π–acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye‐X (X=F, Cl, Br, and I) was immobilized on a TiO 2 surface to investigate how the halogen substituents affect the reaction between the light‐induced charge‐separated state, TiO 2 (e − )/ Dye‐X + , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye‐F < Dye‐Cl < Dye‐Br < Dye‐I . Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ‐hole on the heavier halogens, the differences in dye regeneration kinetics for Dye‐Cl , Dye‐Br , and Dye‐I are ascribed to the extent of halogen bonding with the nucleophilic solution species.},
doi = {10.1002/ange.201510641},
url = {https://www.osti.gov/biblio/1401853}, journal = {Angewandte Chemie},
issn = {0044-8249},
number = 20,
volume = 128,
place = {Germany},
year = {Fri Apr 08 00:00:00 EDT 2016},
month = {Fri Apr 08 00:00:00 EDT 2016}
}

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