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http://hdl.handle.net/1942/25561
Title: | Spectral-Luminescent Properties of Meso-Tetraarylporphyrins Revisited: the Role of Aryl Type, Substitution Pattern and Macrocycle Core Protonation | Authors: | Vershilovskaya, Irina V. Stefani, Stefano VERSTAPPEN, Pieter Ngo, Thien H. Scheblykin, Ivan G. Dehaen, Wim MAES, Wouter Kruk, Mikalai M. |
Issue Date: | 2017 | Source: | Macroheterocycles, 10(3), p. 257-267 | Abstract: | Both the ground (S0) and the lowest singlet excited states (S1) for a series of 5,10,15,20-tetraarylporphyrins consisting of two symmetrically and four asymmetrically substituted derivatives (A4, AB3, trans-A2B2, cis-A2B2, A3B and B4, where A=phenyl and B=mesityl) are studied by absorption and fluorescence spectroscopies. The rotational degree of freedom of the aryl rings is found to play a crucial role in the discrimination between the radiative and radiationless decays of the S1 states. This feature is dramatically enhanced upon going from the free base molecules to their mono- and diprotonated forms because of the nonplanar macrocycle conformation of the latters. The progressive A to B replacement of the aryl substituents leads to additive spectral changes over the whole series in the free base form. For both mono- and diprotonated species such a gradual additive pattern is broken by a “spectral jump” from the trans to the cis derivative, which is proposed to be a signature of the transition between two macrocycle conformations with different flexibility. | Keywords: | Porphyrin; meso-substitution; fluorescence; protonation; macrocycle conformation | Document URI: | http://hdl.handle.net/1942/25561 | ISSN: | 1998-9539 | e-ISSN: | 1998-9539 | DOI: | 10.6060/mhc160962n | ISI #: | 000422740500001 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2019 |
Appears in Collections: | Research publications |
Files in This Item:
File | Description | Size | Format | |
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mhc160962n.pdf | Published version | 1.35 MB | Adobe PDF | View/Open |
Macroheterocycles.pdf | Peer-reviewed author version | 857.79 kB | Adobe PDF | View/Open |
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