A novel route to ladder-type structures based on hemiporphyrazines

Abstract

Ladder oligomers with two or three nickel hemiporphyrazine units are synthesized via Diels-Alder reaction, using intermediates with isobenzofuran moieties as diene components.

Stepwise Synthesis of Substituted Dicyanotriazolehemiporphyrazines. A Regioselective Approach to Unsymmetrically Substituted Hemiporphyrazines

“…The very low-field resonance of the inner protons of the triazolehemiporphyrazine core is consistent with the antiaromaticity of these compounds 1a. The same kind of protons appear in the 1 H NMR spectra of structurally related aromatic phthalocyanines at very high field (ca.…”

“…Hemiporphyrazines, two-dimensional π-conjugated macrocycles related to phthalocyanines, have been proposed as targets for the construction of semiconducting 1c,d,3 and nonlinear optical materials …”

“…Although symmetrically substituted hemiporphyrazines are well documented, , there are no reports on the selective preparation of unsymmetrically substituted compounds . Thus, for example, the one-step statistical condensation of two differently substituted diiminoisoindolines with an adequate diaminoheteroaromatic compound (e.g., 2,5-diamino-1,2,4-triazole) affords a mixture of the corresponding statistical distribution compounds…”

“…The preparation of these compounds is interesting, not only from a preparative point of view but also because this kind of non-centrosymmetric conjugated macrocycles with a “push−pull” substitution pattern are targets for the study of second-order nonlinear optical properties 1c,d,

…”