When push comes to shove: unravelling the mechanism and scope of nonemissive meso-unsaturated BODIPY dyes

The Journal of Physical Chemistry. B
Richard LincolnGonzalo Cosa

Abstract

We report herein spectroscopy and computational results that illustrate an efficient intramolecular deactivation pathway for meso-unsaturated boron-dipyrromethene (BODIPY) dyes in their singlet excited state. Our results show that the mechanism hinges on the structural flexibility imparted by the boron atom and on the energetic stabilization conferred by extending the conjugation into the meso substituent, which is otherwise unconjugated in the ground state. Following photoexcitation, rotation along the dihedral angle of the meso-unsaturated group results in its conjugation at the expense of shifting one pyrrole moiety in dipyrrin out of the plane. Internal conversion to an energetically hot, ground-state species efficiently competes with emission. The mechanism applies to meso-vinyl, -formyl, and -iminyl moieties. The presence of methyl groups at positions C1 and C7 exacerbates the energetic penalty toward conjugation of the meso groups leading to a small energy gap between relaxed excited state and ground state and undetected emission quantum yields. Importantly, methyls at C1 and C7 prevent nonradiative deactivation in meso-aryl moieties, illustrating that when push comes to shove, the energetic (kinetic) barrier toward reac...Continue Reading

References

Jul 21, 2006·The Journal of Physical Chemistry. B·Hooi Ling KeeDewey Holten
Jul 27, 2006·Journal of the American Chemical Society·Aaron E AlbersChristopher J Chang
Oct 11, 2007·Chemical Reviews·Aurore Loudet, Kevin Burgess
May 7, 2008·Journal of the American Chemical Society·Marina K KuimovaKlaus Suhling
Apr 15, 2009·The Journal of Organic Chemistry·Katerina KrumovaGonzalo Cosa
Sep 3, 2009·The Journal of Organic Chemistry·Lijuan JiaoErhong Hao
Apr 7, 2010·Journal of the American Chemical Society·Bryan C DickinsonChristopher J Chang
Mar 5, 2011·The Journal of Organic Chemistry·Takuya MatsumotoTetsuo Nagano
Oct 14, 2011·Organic Letters·Neelam ShivranSubrata Chattopadhyay
Jun 15, 2012·Angewandte Chemie·Jun YangNeal K Devaraj
Nov 24, 2012·Nature Chemistry·Jefferson ChanChristopher J Chang
Dec 21, 2012·Journal of the American Chemical Society·Nathaniel I ShankBruce A Armitage
Jan 23, 2013·Angewandte Chemie·André Nadler, Carsten Schultz
Oct 12, 2013·Journal of the American Chemical Society·Katerina KrumovaGonzalo Cosa
Mar 7, 2014·Chemistry : a European Journal·Hao ZhuXiaojun Peng
Apr 24, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhong-Hua PanRui-Bo Wu
May 27, 2014·Nature Methods·Gražvydas LukinavičiusKai Johnsson

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Citations

Jul 4, 2019·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Richard LincolnGonzalo Cosa
Nov 29, 2016·Physical Chemistry Chemical Physics : PCCP·Antonio PrljClemence Corminboeuf
Sep 25, 2018·Angewandte Chemie·Chamari S WijesooriyaEmily A Smith
Jan 16, 2021·The Journal of Organic Chemistry·Tyll FreeseDaniel B Werz
Sep 28, 2017·Journal of the American Chemical Society·Lukas J PatalagDaniel B Werz
Aug 9, 2018·ACS Omega·Diana E Ramírez-OrnelasEduardo Peña-Cabrera
Oct 5, 2017·Journal of the American Chemical Society·Richard LincolnGonzalo Cosa
Jan 6, 2022·ACS Sensors·Richard LincolnGonzalo Cosa

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