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Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids
- Source :
- Molecules : A Journal of Synthetic Chemistry and Natural Product Chemistry, Woller, T, Geerlings, P, De Proft, F, Champagne, B & Alonso, M 2018, ' Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids ', Molecules, vol. 23, no. 6, 1333, pp. 1333 . https://doi.org/10.3390/molecules23061333, Molecules, Vol 23, Iss 6, p 1333 (2018), Molecules, Volume 23, Issue 6
- Publication Year :
- 2018
- Publisher :
- Multidisciplinary Digital Publishing Institute (MDPI), 2018.
-
Abstract
- With their versatile molecular topology and aromaticity, porphyrinoid systems combine remarkable chemistry with interesting photophysical properties and nonlinear optical properties. Hence, the field of application of porphyrinoids is very broad ranging from near-infrared dyes to opto-electronic materials. From previous experimental studies, aromaticity emerges as an important concept in determining the photophysical properties and two-photon absorption cross sections of porphyrinoids. Despite a considerable number of studies on porphyrinoids, few investigate the relationship between aromaticity, UV/vis absorption spectra and nonlinear properties. To assess such structure-property relationships, we performed a computational study focusing on a series of H&uuml<br />ckel porphyrinoids to: (i) assess their (anti)aromatic character<br />(ii) determine the fingerprints of aromaticity on the UV/vis spectra<br />(iii) evaluate the role of aromaticity on the NLO properties. Using an extensive set of aromaticity descriptors based on energetic, magnetic, structural, reactivity and electronic criteria, the aromaticity of [4n+2] &pi<br />electron porphyrinoids was evidenced as was the antiaromaticity for [4n] &pi<br />electron systems. In agreement with previous studies, the absorption spectra of aromatic systems display more intense B and Q bands in comparison to their antiaromatic homologues. The nature of these absorption bands was analyzed in detail in terms of polarization, intensity, splitting and composition. Finally, quantities such as the average polarizability and its anisotropy were found to be larger in aromatic systems, whereas first and second hyperpolarizability are influenced by the interplay between aromaticity, planarity and molecular symmetry. To conclude, aromaticity dictates the photophysical properties in porphyrinoids, whereas it is not the only factor determining the magnitude of NLO properties.
- Subjects :
- Porphyrins
Absorption spectroscopy
Hyperpolarizability
Pharmaceutical Science
nonlinear optical properties
Porphyrinoids
010402 general chemistry
01 natural sciences
Article
Analytical Chemistry
lcsh:QD241-441
Structure-Activity Relationship
lcsh:Organic chemistry
Isomerism
Polarizability
Ultraviolet/methods
Drug Discovery
Molecular symmetry
Physical and Theoretical Chemistry
Absorption (electromagnetic radiation)
Spectrophotometry, Ultraviolet/methods
010405 organic chemistry
Aromaticity
Organic Chemistry
Absorption spectra
Porphyrins/chemistry
Planarity testing
0104 chemical sciences
Nonlinear Dynamics
Chemical physics
Chemistry (miscellaneous)
Spectrophotometry
Molecular Medicine
Anisotropy
Spectrophotometry, Ultraviolet
aromaticy
Antiaromaticity
Subjects
Details
- Language :
- English
- ISSN :
- 14203049 and 14315165
- Volume :
- 23
- Issue :
- 6
- Database :
- OpenAIRE
- Journal :
- Molecules
- Accession number :
- edsair.doi.dedup.....6bf3a1835b7e991a7d0b0f0fd6aed892