Boron-Templated Synthesis of B(III)-Submonoazaporphyrins: The Hybrids of B(III)-Subporphyrins and B(III)-Subporphyrazines.

Abstract

A new class of hybridized and core-contracted porphyrinoids, B(III)-submonoazaporphyrins, which may be viewed as the hybrids of B(III)-subporphyrins and B(III)-subporphyrazines, was reported. The versatile single-step synthesis was based on an efficient intramolecular nucleophilic substitution reaction on readily available α-amino-α'-bromotripyrromethenes, while boronic acids, trifluoroborate salts, or trimethoxyborate simultaneously acted as the template and provider of apical substituent. Those new hybrids, as robust and photostable compounds, were fully characterized by NMR, mass spectrometry, and X-ray crystallography. They showed intense absorption and emission in the visible region, and their electrochemical properties and computational calculation are also discussed.