A theoretical survey of the UV–visible spectra of axially and peripherally substituted boron subphthalocyanines
The UV–visible spectra of a series of subphthalocyanines (SubPcs) characterized by three different axial substituents (An ) in combination with H, F, NO2, SO2 H and SO2 CH3 peripheral substituents (Ri ) were predicted and analyzed by means of time-dependent DFT calculations, including chloroform as...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/706806 |
| Acceso en línea: | http://hdl.handle.net/10486/706806 https://dx.doi.org/10.3390/computation10020014 |
| Access Level: | acceso abierto |
| Palabra clave: | Axial substituents Peripheral substituents Subphthalocyanines Time-dependent DFT UV–visible spectra Química |
| Sumario: | The UV–visible spectra of a series of subphthalocyanines (SubPcs) characterized by three different axial substituents (An ) in combination with H, F, NO2, SO2 H and SO2 CH3 peripheral substituents (Ri ) were predicted and analyzed by means of time-dependent DFT calculations, including chloroform as a solvent. In this analysis, we paid particular attention to the Q band, which remained almost unchanged regardless of the nature of the axial substituent. For the same axial substituent, changes in the Q band were also rather small when hydrogens at the periphery were replaced by R1 = SO2 H and R1 = R2 = SO2 H. However, the shifting of the Q band was almost 10 times larger when R1 = NO2 and R1 = R2 = NO2 due to the participation of this substituent in the π SubPc cloud. In most cases, the characteristics of the spectra can be explained considering only the transitions involving the HOMO-1, HOMO, LUMO and LUMO + 1 orbitals, where the Q band can be decomposed into two main contributions, leading to charge separation. Only for SubPc(A3,F,F,H) would one of the two contributions from the deepest orbital involved not lead to charge transfer. For this latter case, the HOMO-2 orbital must also be taken into account. In summary, the results obtained with the analysis of the MO indicate that the studied SubPcs are appropriate for photochemical devices |
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