Bulky Substituents Promote Triplet-Triplet Annihilation Over Triplet Excimer Formation in Naphthalene Derivatives
Journal article, 2023

Visible-to-ultraviolet (UV) triplet-triplet annihilation photochemical upconversion (TTA-UC) has gained a lot of attention recently due to its potential for driving demanding high-energy photoreactions using low-intensity visible light. The efficiency of this process has rapidly improved in the past few years, in part thanks to the recently discovered annihilator compound 1,4-bis((triisopropylsilyl)ethynyl)naphthalene (N-2TIPS). Despite its beneficial TTA-UC characteristics, the success of N-2TIPS in this context is not yet fully understood. In this work, we seek to elucidate what role the specific type and number of substituents in naphthalene annihilator compounds play to achieve the characteristics sought after for TTA-UC. We show that the type of substituent attached to the naphthalene core is crucial for its performance as an annihilator. More specifically, we argue that the choice of substituent dictates to what degree the sensitized triplets form excimer complexes with ground state annihilators of the same type, which is a process competing with that of TTA. The addition of more bulky substituents positively impacts the upconverting ability by impeding excimer formation on the triplet surface, an effect that is enhanced with the number of substituents. The presence of triplet excimers is confirmed from transient absorption measurements, and the excimer formation rate is quantified, showing several orders of magnitude differences between different derivatives. These insights will aid in the further development of annihilator compounds for solar energy applications for which the behavior at low incident powers is of particular significance.

Author

Axel Olesund

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Shima Ghasemi

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Kasper Moth-Poulsen

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Bo Albinsson

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Journal of the American Chemical Society

0002-7863 (ISSN) 1520-5126 (eISSN)

Vol. 145 40 22168-22175

Photon upconversion under diffusion-free conditions: Breaking the Shockley-Queisser limit for solar energy devices

Swedish Energy Agency (46526-1), 2019-01-01 -- 2023-12-31.

Subject Categories

Materials Chemistry

Other Physics Topics

Organic Chemistry

DOI

10.1021/jacs.3c08115

PubMed

37766514

More information

Latest update

10/27/2023