Synthesis, Photophysical Properties, andAb InitioCalculations of 2-(2-Hydroxy/methoxyphenyl)pyrimidines Substituted by Sterically Hindered Electron-Donating Groups
Abstract
A series of 2-(2-hydroxyphenyl)pyrimidines bearing sterically hindered electron-donating groups (DMAC, PXZ, PTZ, and NPh2), together with their methoxy precursors, were synthesized and investigated by photophysical studies and ab initio calculations. While the hydroxy derivatives were essentially nonemissive due to efficient nonradiative deactivation associated with excited-state intramolecular proton transfer (ESIPT) processes, the methoxy analogues displayed clear fluorescence and positive solvatochromism, consistent with an intramolecular charge transfer (ICT) character. The emission properties strongly depended on the donor nature and substitution pattern, with NPh2 derivatives showing the highest fluorescence quantum yields. Theoretical calculations revealed that steric effects and twisted donor-acceptor geometries govern the balance between ICT, ESIPT, and radiative pathways. These results provide valuable insights for the design of pyrimidine-based color-tunable fluorophores.
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BibTeX
@article{diguet2026synthesis,
title = {{Synthesis, Photophysical Properties, andAb InitioCalculations of 2-(2-Hydroxy/methoxyphenyl)pyrimidines Substituted by Sterically Hindered Electron-Donating Groups}},
author = {Clément Diguet and Angela Dellai and Adèle D. Laurent and Julien Massue and Françoise Robin-Le Guen and Sébastien Gauthier and Sylvain Achelle},
journal = {Journal of Organic Chemistry},
year = {2026},
month = sep,
doi = {10.1021/acs.joc.6c01185},
url = {https://hal.science/hal-05789603v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Synthesis, Photophysical Properties, andAb InitioCalculations of 2-(2-Hydroxy/methoxyphenyl)pyrimidines Substituted by Sterically Hindered Electron-Donating Groups
AU - Clément Diguet
AU - Angela Dellai
AU - Adèle D. Laurent
AU - Julien Massue
AU - Françoise Robin-Le Guen
AU - Sébastien Gauthier
AU - Sylvain Achelle
PY - 2026
DA - 2026/09/25
JO - Journal of Organic Chemistry
DO - 10.1021/acs.joc.6c01185
UR - https://hal.science/hal-05789603v1
AB - A series of 2-(2-hydroxyphenyl)pyrimidines bearing sterically hindered electron-donating groups (DMAC, PXZ, PTZ, and NPh2), together with their methoxy precursors, were synthesized and investigated by photophysical studies and ab initio calculations. While the hydroxy derivatives were essentially nonemissive due to efficient nonradiative deactivation associated with excited-state intramolecular proton transfer (ESIPT) processes, the methoxy analogues displayed clear fluorescence and positive solvatochromism, consistent with an intramolecular charge transfer (ICT) character. The emission properties strongly depended on the donor nature and substitution pattern, with NPh2 derivatives showing the highest fluorescence quantum yields. Theoretical calculations revealed that steric effects and twisted donor-acceptor geometries govern the balance between ICT, ESIPT, and radiative pathways. These results provide valuable insights for the design of pyrimidine-based color-tunable fluorophores.
SN - 0022-3263
SN - 1520-6904
ER -