dc.contributor.author | Senge, Mathias | |
dc.date.accessioned | 2025-01-14T09:59:56Z | |
dc.date.available | 2025-01-14T09:59:56Z | |
dc.date.issued | 2024 | |
dc.date.submitted | 2024 | en |
dc.identifier.citation | Orzanowska, G. and Ryppa, C. and Senge, M.O. and Waluk, J., Fine-tuning of radiative properties by “mild” substituents: searching for a perfectly soft chromophore, Physical Chemistry Chemical Physics, 26, 25, 2024, 17944-17950 | en |
dc.identifier.other | Y | |
dc.description.abstract | Controlling spectral properties to achieve desired characteristics is an attractive goal in application-
oriented research, e.g., in the design of fluorescence sensors. ‘‘Soft’’ chromophores, molecules with
strong spectral responses to internal or external perturbations are good candidates for such studies. In
this work, absorption, fluorescence, and magnetic circular dichroism (MCD) spectra were obtained for a
series of porphyrins, substituted at the meso-positions with n-hexyl groups. As the number of
substituents increases from 1 to 4, significant changes are observed. The intensity of the S0 –S 1 transition
(Qx) in the 0–0 region strongly decreases in mono-substituted porphyrin, but upon additional substitutions it increases to values larger than in the parent, unsubstituted molecule. Such behavior can be
explained, using the perimeter model, by changes in the energy splittings between the two highest
(HOMO) and two lowest (LUMO) frontier molecular orbitals. Single substitution makes porphyrin a nearly
perfect soft chromophore, but upon introduction of a larger number of n-hexyl groups it is transformed
into a hard one. DFT simulations incorrectly predict a continuous transition from a soft to hard chromophore, because the calculated ordering of two HOMO orbitals is opposite to that obtained by experiment. On the other hand, for those porphyrins that can be classified as hard chromophores, the
calculations nicely reproduce contributions of Franck–Condon and Herzberg–Teller terms to absorption
and fluorescence spectra. | en |
dc.format.extent | 17944-17950 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Physical Chemistry Chemical Physics; | |
dc.relation.ispartofseries | 26; | |
dc.relation.ispartofseries | 25; | |
dc.rights | Y | en |
dc.title | Fine-tuning of radiative properties by “mild” substituents: searching for a perfectly soft chromophore | en |
dc.type | Journal Article | en |
dc.type.supercollection | scholarly_publications | en |
dc.type.supercollection | refereed_publications | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/sengem | |
dc.identifier.rssinternalid | 271425 | |
dc.identifier.doi | http://dx.doi.org/10.1039/d4cp01502a | |
dc.rights.ecaccessrights | openAccess | |
dc.identifier.orcid_id | 0000-0002-7467-1654 | |
dc.identifier.uri | https://hdl.handle.net/2262/110648 | |