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Herein, three [2 + 2]-type porphyrins and their Zn(II)-complexes with various  meso -substitutions have been synthesized and characterized. Analysis of the electronic structures was carried out by comparing the spectroscopic investigations and electrochemical characterizations. These porphyrins have tunable aggregated morphologies modulated by  meso -substituents and metal-cation in the coordination center of the tetrapyrrolic macrocycle.

Tuning the molecular electronic structure and macroscopic aggregates of [2 + 2]-type H 2 - and Zn(II)porphyrins through meso -substituents