Naslov
1,3-Diradicals Embedded in Curved Paraphenylene Units: Singlet versus Triplet State and In-Plane Aromaticity

Autori
Miyazawa, Yuki ; Wang, Zhe ; Matsumoto, Misaki ; Hatano, Sayaka ; Antol, Ivana ; Kayahara, Eiichi ; Yamago, Shigeru ; Abe, Manabu

Izvornik
Journal of the American Chemical Society (0002-7863) 143 (2021), 19; 7426-7439

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
1, 3-diradicals ; curved paraphenylenes

Sažetak
Curved π-conjugated molecules and open-shell structures have attracted much attention from the perspective of fundamental chemistry, as well as materials science. In this study, the chemistry of 1, 3-diradicals (DRs) embedded in curved cycloparaphenylene (CPPs) structures, DR- (n+3)CPPs (n = 0–5), was investigated to understand the effects of the curvature and system size on the spin–spin interactions and singlet versus triplet state, as well as their unique characteristics such as in-plane aromaticity. A triplet ground state was predicted for the larger 1, 3-diradicals, such as the seven- and eight-paraphenylene-unit-containing diradicals DR-7CPP (n = 4) and DR-8CPP (n = 5), by quantum chemical calculations. The smaller- sized diradicals DR-(n+3)CPPs (n = 0–3) were found to possess singlet ground states. Thus, the ground-state spin multiplicity is controlled by the size of the paraphenylene cycle. The size effect on the ground-state spin multiplicity was confirmed by the experimental generation of DR- 6CPP in the photochemical denitrogenation of its azo-containing precursor (AZ-6CPP). Intriguingly, a unique type of in-plane aromaticity emerged in the smaller-sized singlet states such as S-DR- 4CPP (n = 1), as proven by nucleus-independent chemical shift calculations (NICS) and an analysis of the anisotropy of the induced current density (ACID), which demonstrate that homoconjugation between the 1, 3-diradical moiety arises because of the curved and distorted bonding system.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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