It Takes More Than an Imine: The Role of the Central Atom on the Electron-Accepting Ability of Benzotriazole and Benzothiadiazole Oligomers

• Published in: Journal of the American Chemical Society 2012-02, Vol.134 (5), p.2599-2612
• Main Authors: Patel, Dinesh G. (Dan), Feng, Fude, Ohnishi, Yu-ya, Abboud, Khalil A, Hirata, So, Schanze, Kirk S, Reynolds, John R
• Format: Article
• Language: English
• Subjects: Electrons; Imines - chemistry; Molecular Structure; Quantum Theory; Stereoisomerism; Thiadiazoles - chemistry; Triazoles - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja207978v

We report on the comparison of the electronic and photophysical properties of a series of related donor–acceptor–donor oligomers incorporating the previously known 2H-benzo[d][1,2,3]triazole (BTz) moiety as the acceptor and the recently reported BTzTD acceptor, a hybrid of BTz and 2,1,3-benzothiadiazole (BTD). Although often implied in the polymer literature that BTz has good acceptor character, we show that this moiety is best described as a weak acceptor. We present electrochemical, computational, and photophysical evidence supporting our assertion that BTzTD is a strong electron acceptor while maintaining the alkylation ability of the BTz moiety. Our results show that the identity of the central atom (N or S) in the benzo-fused heterocyclic ring plays an important role in both the electron-accepting and the electron-donating ability of acceptor moieties with sulfur imparting a greater electron-accepting ability and nitrogen affording greater electron-donating character. We report on the X-ray crystal structure of a BTzTD trimer, which exhibits greater local aromatic character in the region of the triazole ring and contains an electron-deficient sulfur that imparts strong electron-accepting ability. Additionally, we examine the transient absorption spectra of BTzTD and BTz oligomers and report that the BTz core promotes efficient intersystem crossing to the triplet state, while the presence of the thiadiazole moiety in BTzTD leads to a negligible triplet yield. Additionally, while BTz does not function as a good acceptor, oligomers containing this moiety do function as excellent sensitizers for the generation of singlet oxygen.