Direct Synthesis of ABCD‐Porphyrin Platinum(II) Complexes via Dehydrative Aromatization

Abstract

Since the development of the first method for porphyrin synthesis by Rothemund in 1935, porphyrin derivatives have been widely investigated and have played an essential role in chemical sciences. Most synthetic routes of porphyrins involve oxidative aromatization. Herein, we present a synthetic method to produce ABCD‐porphyrins, including chiral ones, through a one‐pot reaction involving “coordination, cyclization, and dehydrative aromatization” using a mono‐dipyrrinatoPt(II)Cl(COE) (COE = cyclooctene) complex as a platinum template.

Pt–S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S^C^N^O) Complexes

“…To understand the absorption and emission origins of the Pt­(S^C^N^O) complexes, DFT and time-dependent DFT (TD-DFT) calculations were performed at the MN15/6-31G­(d)/LANL2DZ level. − The optimized ground state (S 0 ) and selected structural parameters of PtSZ and PtSZtBu are provided in Table S4, which are consistent with the X-ray crystal structure analysis discussed earlier. The HOMOs of the Pt­(S^C^N^O) complexes mainly reside on the π phenolate and d Pt orbitals, with some contribution from the π ph‑pyridine orbitals (Figure c).…”