Synthesis and Photophysics of Phenylene Based Triplet Donor–Acceptor Dyads: ortho vs. para Positional Effect on Intramolecular Triplet Energy Transfer

• DOI: 10.1016/j.jpap.2022.100112
• Publication Date: 2022-02-08T22:47:17Z
• Authors: Young Ju Yun; Manoj K. Manna; Nareshbabu Kamatham; Jingbai Li; Shuyang Liu; Francesca Peccati; Barry C. Pemberton; Gary P. Wiederrecht; David J. Gosztola; Gonzalo Jiménez-Osés; Andrey Yu Rogachev; A. Jean-Luc Ayitou
• Keywords: Chemistry; Charge transfer; Triplet energy transfer; Triplet-triplet annihilation; Triplet photochemistry; 02 engineering and technology; 0210 nano-technology; QD1-999; bichromophores

ABSTRACT: Two phenylene based geometrical/isomeric triplet ortho- and para–dyads (o–3 and p–3, respectively) were synthesized and fully characterized using advanced photophysical tools and computations. In dyad o–3, the through-space donor-acceptor interactions led to simultaneous triplet energy transfer and charge transfer with identical kinetics. On the other hand, in the dyad p–3, it was found that the phenylene spacer favors a fast triplet energy delocalization over the charge transfer process. Furthermore, analysis of the results from the present investigation indicates that the deactivation of the photo-excited species (o–3)* occurs through both the intrinsic channel viz. S0←S1 and charge recombination. In the case of dyad p–3, the results indicate that the primary deactivation pathway is self-quenching or triplet-triplet annihilation involving the acceptor unit(s).