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Spectral-luminescent properties of meso-tetraarylporphyrins revisited : The role of aryl type, substitution pattern and macrocycle core protonation

Vershilovskaya, Irina V.; Stefani, Stefano; Verstappen, Pieter; Ngo, Thien H.; Scheblykin, Ivan G. LU ; Dehaen, Wim; Maes, Wouter and Kruk, Mikalai M. (2017) In 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... (More)

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.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Fluorescence, Macrocycle conformation, Meso-substitution, Porphyrin, Protonation
in
Macroheterocycles
volume
10
issue
3
pages
11 pages
publisher
Ivanovo State Univ Chemical Technology
external identifiers
  • scopus:85038073174
ISSN
1998-9539
DOI
10.6060/mhc160962n
language
English
LU publication?
yes
id
f2783064-8056-4c36-b6f2-458d9a74079b
date added to LUP
2018-01-05 07:31:30
date last changed
2018-01-05 07:31:30
@article{f2783064-8056-4c36-b6f2-458d9a74079b,
  abstract     = {<p>Both the ground (S<sub>0</sub>) and the lowest singlet excited states (S<sub>1</sub>) for a series of 5,10,15,20-tetraarylporphyrins consisting of two symmetrically and four asymmetrically substituted derivatives (A<sub>4</sub>, AB<sub>3</sub>, trans-A<sub>2</sub>B<sub>2</sub>, cis-A<sub>2</sub>B<sub>2</sub>, A<sub>3</sub>B and B<sub>4</sub>, 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 S<sub>1</sub> 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.</p>},
  author       = {Vershilovskaya, Irina V. and Stefani, Stefano and Verstappen, Pieter and Ngo, Thien H. and Scheblykin, Ivan G. and Dehaen, Wim and Maes, Wouter and Kruk, Mikalai M.},
  issn         = {1998-9539},
  keyword      = {Fluorescence,Macrocycle conformation,Meso-substitution,Porphyrin,Protonation},
  language     = {eng},
  number       = {3},
  pages        = {257--267},
  publisher    = {Ivanovo State Univ Chemical Technology},
  series       = {Macroheterocycles},
  title        = {Spectral-luminescent properties of meso-tetraarylporphyrins revisited : The role of aryl type, substitution pattern and macrocycle core protonation},
  url          = {http://dx.doi.org/10.6060/mhc160962n},
  volume       = {10},
  year         = {2017},
}