Zinc Tetrabenzotriazaporphyrins: Improved Synthesis, Structural Analysis and Photophysical Properties
Abstract
Tetrabenzotriazaporphyrin (TBTAP) is a relatively unexplored hybrid macrocycle that occupies a unique structural position between porphyrins and phthalocyanines, featuring the replacement of one of the four aza bridges of the phthalocyanine framework by a methine group. Herein, we report a novel synthetic methodology based on the condensation of phosphonium salts (phenyl substituent is ortho-substituted by H or Me or CN) with phthalonitrile in Dowtherm A™, providing access to three zinc TBTAPs in improved yields. This approach is readily amenable to scale-up and exhibits broad functional-group tolerance, accommodating both electrondonating and electron-withdrawing substituents, as well as sterically demanding orthosubstituted aromatic rings. The structures were determined by X-Ray diffraction and the absorption and steady state and time resolved fluorescence properties were measured. Time-Dependent Density Functional Theory (TD-DFT) calculations rationalized the change in the absorption Q-bands. These results provide a solid foundation for the further development and systematic exploration of this largely unexplored class of dyes.
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BibTeX
@article{defferrari2026zinc,
title = {{Zinc Tetrabenzotriazaporphyrins: Improved Synthesis, Structural Analysis and Photophysical Properties}},
author = {Diego Defferrari and Simon Pascal and Stéphane Diring and Denis Jacquemin and Fabrice Odobel},
journal = {Dyes and Pigments},
year = {2026},
month = oct,
doi = {10.1016/j.dyepig.2026.114276},
url = {https://hal.science/hal-05791659v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Zinc Tetrabenzotriazaporphyrins: Improved Synthesis, Structural Analysis and Photophysical Properties
AU - Diego Defferrari
AU - Simon Pascal
AU - Stéphane Diring
AU - Denis Jacquemin
AU - Fabrice Odobel
PY - 2026
DA - 2026/10/09
JO - Dyes and Pigments
DO - 10.1016/j.dyepig.2026.114276
UR - https://hal.science/hal-05791659v1
AB - Tetrabenzotriazaporphyrin (TBTAP) is a relatively unexplored hybrid macrocycle that occupies a unique structural position between porphyrins and phthalocyanines, featuring the replacement of one of the four aza bridges of the phthalocyanine framework by a methine group. Herein, we report a novel synthetic methodology based on the condensation of phosphonium salts (phenyl substituent is ortho-substituted by H or Me or CN) with phthalonitrile in Dowtherm A™, providing access to three zinc TBTAPs in improved yields. This approach is readily amenable to scale-up and exhibits broad functional-group tolerance, accommodating both electrondonating and electron-withdrawing substituents, as well as sterically demanding orthosubstituted aromatic rings. The structures were determined by X-Ray diffraction and the absorption and steady state and time resolved fluorescence properties were measured. Time-Dependent Density Functional Theory (TD-DFT) calculations rationalized the change in the absorption Q-bands. These results provide a solid foundation for the further development and systematic exploration of this largely unexplored class of dyes.
SN - 0143-7208
ER -