Tunable Emission and Structural Insights of 6-Arylvinyl-2,4-bis(2′-hydroxyphenyl)pyrimidines and Their O∧N∧O-Chelated Boron Complexes

  1. Plaza-Pedroche, Rodrigo 2
  2. Fernández-Liencres, M. Paz 3
  3. Jiménez-Pulido, Sonia B. 1
  4. Illán-Cabeza, Nuria A. 1
  5. Achelle, Sylvain 4
  6. Navarro, Amparo 3
  7. Rodríguez-López, Julián 2
  1. 1 Departamento de Química Inorgánica y Orgánica, Facultad de Ciencias Experimentales, Universidad de Jaén, Campus Las Lagunillas, 23071 Jaén, Spain
  2. 2 Universidad de Castilla-La Mancha, Área de Química Orgánica, Facultad de Ciencias y Tecnologías Químicas, Avda. Camilo José Cela 10, 13071 Ciudad Real, Spain
  3. 3 Departamento de Química Física y Analítica, Facultad de Ciencias Experimentales, Universidad de Jaén, Campus Las Lagunillas, 23071 Jaén, Spain
  4. 4 Univ. Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR), UMR 6226, F-35000 Rennes, France
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Revista:
ACS Applied Optical Materials

ISSN: 2771-9855,  2771-9855

Ano de publicación: 2024

Tipo: Artigo

DOI: 10.1021/ACSAOM.4C00251 GOOGLE SCHOLAR lock_openAcceso aberto editor

Outras publicacións en: ACS Applied Optical Materials

Resumo

In this study, we present the synthesis and photophysical characteristics of a novel series of 6-arylvinyl-2,4-bis(2′-hydroxyphenyl)pyrimidines. These compounds exhibit nonemissive properties attributed to the potential occurrence of a excited-state intramolecular proton transfer process from the OH groups to the nitrogen atoms of the pyrimidine ring. The introduction of an acid for protonation of the pyrimidine ring results in a significant enhancement of the fluorescence response, easily perceptible to the naked eye. Notably, these molecules serve as intriguing rigid O∧N∧O ligands for boron chelation. The incorporation of boron atoms promotes structural planarity, increases rigidity, and successfully restores fluorescence in both solution and the solid state. Moreover, the photoluminescence was found to be strongly influenced by the nature of the end groups on the arylvinylene fragment, allowing for the modulation of the emission color and covering the optical spectrum from blue to red. Strong emission solvatochromism was observed in various solvents, a finding that supports the formation of intramolecular charge-separated emitting states, particularly when terminal electron-donating groups are present in the structure. X-ray diffraction analysis enables the determination of inter- and intramolecular interactions, as well as molecular packing structures, aiding in the rationalization of distinct luminescent behaviors in the solid state. All experimental findings are elucidated through extensive density functional theory (DFT) and time-dependent DFT calculations.

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