Triplet Formation and Triplet‐Triplet Annihilation Upconversion in Iodine Substituted Non‐Orthogonal BODIPY‐Perylene Dyads - Publication - Bridge of Knowledge

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Triplet Formation and Triplet‐Triplet Annihilation Upconversion in Iodine Substituted Non‐Orthogonal BODIPY‐Perylene Dyads

Abstract

BODIPY-perylene dyads have emerged as useful metal free sensitizers for triplet-triplet annihilation upconversion (TTAUC), these dyads are capable of efficient triplet generation via spinorbit charge transfer intersystem crossing (SOCT-ISC). This important route to triplet formation requires dyads in which two moieties are oriented perpendicular to each other. In this contribution, we give a deeper insight on the behavior of recently reported BODIPY-perylene dyads, where BODIPY-perylene dihedral exhibits a non-orthogonal dyad geometry. The intersystem crossing of BODIPY-perylene dyads with and without iodine are investigated using femtosecond transient absorption (fs-TA) and nanosecond transient absorption (ns-TA) spectroscopy. The concurrent decay of the singlet charge transfer state (1CT) and rise of triplet states in both the iodinated and non-iodinated dyads confirms the SOCT-ISC as the main intersystem crossing pathway despite the altered geometry of the dyads. The presence of an iodine atom on the BODIPY-moiety enables intersystem crossing 2.6-times faster and provides a higher triplet yield with respect to dyad without iodine. The upconversion quantum yield is 8.4-times higher in the sample containing iodinated dyad as sensitizer and perylene as annihilator. The triplet-triplet energy transfer rate (kTTET) is ~8×10^8 M-1.s-1 for both iodinated and noniodinated sensitizer containing TTAUC systems in 1,4-dioxane.

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DOI:
Digital Object Identifier (open in new tab) 10.1002/cptc.202300073
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Category:
Articles
Type:
artykuły w czasopismach
Published in:
ChemPhotoChem pages 1 - 9,
ISSN: 2367-0932
Language:
English
Publication year:
2023
Bibliographic description:
Kumar Jha K., Prabhakaran A., Sia R. C., Arellano-Reyes R. A., Kumar Sarangi N., Yang T., Kumar K., Kupfer S., Guthmuller J., Keyes T. E., Dietzek-Ivanšić B.: Triplet Formation and Triplet‐Triplet Annihilation Upconversion in Iodine Substituted Non‐Orthogonal BODIPY‐Perylene Dyads// ChemPhotoChem -,iss. 10 (2023), s.1-9
DOI:
Digital Object Identifier (open in new tab) 10.1002/cptc.202300073
Sources of funding:
Verified by:
Gdańsk University of Technology

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