Triplet excited state properties in variable gap π-conjugated donor-acceptor-donor chromophores

Chemical Science
Seda CekliKirk S Schanze

Abstract

A series of variable band-gap donor-acceptor-donor (DAD) chromophores capped with platinum(ii) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet-triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin-orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a ...Continue Reading

References

Jul 24, 2001·Inorganic Chemistry·C E WhittleK S Schanze
Sep 20, 2001·Journal of the American Chemical Society·J S WilsonR H Friend
Oct 17, 2002·Journal of the American Chemical Society·Yao LiuKirk S Schanze
Feb 27, 2003·Journal of the American Chemical Society·Igor V RubtsovMichael J Therien
Apr 20, 2006·Chemical Communications : Chem Comm·Fengqi GuoKirk S Schanze
Dec 15, 2006·The Journal of Physical Chemistry. a·Thomas M CooperJonathan E Slagle
Feb 10, 2009·Journal of the American Chemical Society·Timothy T StecklerJohn R Reynolds
Oct 13, 2009·The Journal of Physical Chemistry. B·Bram P KarstenRené A J Janssen
Nov 12, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Stefan HellströmMats R Andersson
Jan 28, 2009·ACS Applied Materials & Interfaces·Jianguo MeiKirk S Schanze
May 21, 2010·The Journal of Organic Chemistry·Sheng YaoKevin D Belfield
Aug 4, 2010·Physical Chemistry Chemical Physics : PCCP·Mihajlo Etinski, Christel M Marian
Aug 24, 2010·Accounts of Chemical Research·Pierre M BeaujugeJohn R Reynolds
Mar 8, 2011·Journal of the American Chemical Society·Samuel C PriceWei You
Mar 1, 2013·ACS Applied Materials & Interfaces·Anand ParthasarathyKirk S Schanze
Feb 14, 2014·Journal of the American Chemical Society·Ala'a O El-BallouliOmar F Mohammed
Aug 22, 2015·Journal of the American Chemical Society·Longbin RenXiaozhang Zhu

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Citations

Nov 8, 2018·Physical Chemistry Chemical Physics : PCCP·David J StewartJoy E Haley
Jan 31, 2019·Advanced Materials·Bing WangGuillermo C Bazan
Apr 9, 2019·Advanced Materials·Yingzhi JinFengling Zhang
Sep 2, 2020·Journal of the American Chemical Society·Wei-Jian LiHai-Bo Yang
Jun 14, 2016·The Journal of Physical Chemistry. a·Seda CekliKirk S Schanze
May 6, 2017·The Journal of Organic Chemistry·Yanbing ZhangJared H Delcamp
Jan 18, 2018·Journal of the American Chemical Society·Qinglai YangHongjie Dai
May 3, 2018·Journal of the American Chemical Society·Shahnawaz RafiqGregory D Scholes

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Methods Mentioned

BETA
Fluorescence
phosphorescence

Software Mentioned

Gaussian
FluoFit

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