Ion-Pairing Assemblies of Dithienylnitrophenol-Based π-Electronic Anions Stabilized by Intramolecular Interactions

Abstract

Dithienylnitrophenols were synthesized as precursors of π-electronic anions, which were stabilized by intramolecular chalcogen bonding, forming various ion pairs in combination with cations. The modes of solid-state charge-by-charge assemblies, along with solution-state stacking and photoinduced electron transfer behaviors, were modulated by the constituent ionic species.

π-Electronic ion pairs: building blocks for supramolecular nanoarchitectonics viaiπ–iπ interactions

“…21b(i)). 68 Detailed theoretical studies and single-crystal X-ray analysis of TBA + -35a À revealed intramolecular SÁ Á ÁO À chalcogen bonding (Fig. 21b(ii)).…”

“…43c). 68 As described in Section 2.3, quinone methide units effectively stabilize p-electronic anions. 69 In addition, as represented by Yang's diradical, 97 combinations of multiple quinone methide units can provide open-shell species, whose spin states depend on the bridging unit as spin coupler; however, the ground state of 36 À is closed-shell state.…”

Photoresponsive ion‐pairing assemblies

“…The delocalization of negative charge into the core π‐electronic units is vital for stabilizing these π‐electronic anions. Anionic species resulting from the deprotonation of dipyrrolylnitrophenols 35a , b − [60] and dithienylnitrophenols 36a , b − [61] display intramolecular hydrogen and chalcogen bonding, respectively. This leads to planar geometries, as elucidated by single‐crystal X‐ray analysis and theoretical evaluations (Figure 22a).…”

Triazatriangulenium salts – hosts and guests in supramolecular assemblies in solution

“…15–18 Moreover, these dyes can form heterostacks with other fluorescent dyes showing bright fluorescence emission. 4,7,19–21 However, there is still a gap in understanding how TATA dyes interact with various π-systems in solution and how strong the interactions are.…”