Subazaphenalenephthalocyanine: A Subphthalocyanine Analogue Bearing a Six‐Membered Ring Unit

Abstract

At the core: A novel core‐modified subphthalocyanine analogue has been synthesized (see structure; Cl green, red O, blue N). This molecule comprises a six‐membered ring unit in place of a five‐membered ring unit and exhibits unique spectroscopic (see plot) and electrochemical properties originating from the azaphenalene‐containing 14π‐electron conjugation system.

A Core‐Expanded Subphthalocyanine Analogue with a Significantly Distorted Conjugated Surface and Unprecedented Properties

“…[16] This synthetic strategy also opened access to a SubPc analogue with a six-membered ring in the core; we referred to this analogue as subazaphenalenephthalocyanine (SubAPPc, Scheme 1). [17] The course of our investigation on core expansion of the contracted SubPc structure further resulted in the synthesis of a novel seven-membered-ring-containing SubPc analogue, which exhibited a clear difference in the ring-current effects genuinely arising from the convex and concave surfaces. Furthermore, unique properties originating from the core expansion of the SubPc structures were also Scheme 1.…”

“…Similar packing diagrams were observed for the axially fluoro substituted SubPc and subporphyrazine analogues. [20] The shallower bowl depth of 1 a (0.57 ), as defined by the deviation of the central boron atom from the 3N plane relative to that observed for SubPcs (0.59-0.66 ) [7] and SubAPPc (0.58 ), [17] implies a more planar coordination geometry around the boron atom in 1 a (sum of the N-B-N angles: SubPc, 308-3168; SubAPPc, 317.58; 1 a, 319.98; Scheme 1). Optimized structures of 1 a and 2 a based on DFT calculations at the B3LYP/6-31G(d) level exhibited similar structural features.…”

A computational investigation on core‐expanded subphthalocyanines

“…At present, a large number of experimental and theoretical studies on subPC and its modified derivatives have been performed to alter and explore their optical and physical properties. The modifications of subPC mainly include peripheral, center (boron‐substituted), axial substitution, and core expansion with a six‐ or seven‐membered ring . Among these modifications, the core expansions catch our attention because it is quite new and significantly affects the optical and physical properties of subPC .…”

Subphthalocyanines as electron mediators in biosensors based on phenol oxidases: Application to the analysis of red wines

“…In addition, subphthalocyanine analogues with an extended p-system: (subphthalocyanines [22][23][24], subazaphenalenephthalocyanines [25] and planar bi-and trinuclear subphthalocyanines [26,27]), have been obtained and identified.…”