Electronic structures and solvent effects of unsymmetrical neo-confused porphyrin: DFT and TDDFT–IEFPCM investigations
| Autor: | Hong-Yu Cao, Qian Tang, Ce Hao, Duan-Hui Si, Xue-Fang Zheng |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
Physics::Biological Physics
Absorption spectroscopy 02 engineering and technology Time-dependent density functional theory 010402 general chemistry 021001 nanoscience & nanotechnology Condensed Matter Physics Photochemistry 01 natural sciences Biochemistry Polarizable continuum model Porphyrin 0104 chemical sciences chemistry.chemical_compound chemistry Density functional theory Molecular orbital Physical and Theoretical Chemistry Solvent effects 0210 nano-technology Absorption (electromagnetic radiation) |
| Zdroj: | Computational and Theoretical Chemistry. 1081:18-24 |
| ISSN: | 2210-271X |
| DOI: | 10.1016/j.comptc.2016.01.012 |
| Popis: | Unsymmetrical porphyrin derivatives and metal-coordinated porphyrin have received great attention in potential application for their intriguing photo-physical and photo-chemical properties. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations were applied to simulate the molecular and electronic structures with the electronic absorption spectra of the unsymmetrical neo-confused porphyrin (NeoCP) derivatives. Molecular structure and fragment charge distribution results revealed that the carbon–nitrogen-swap structure lead to the redistribution of charges and the differentiation of inner hydrogen in the Neo-confused Porphyrin ring. Introducing the unsymmetrical strategy onto the porphyrin skeleton effectively varied the energy levels of molecular orbitals, resulting in significant multi-band photon absorption and Soret band splitting for the porphyrin derivatives. Ni coordinated NeoCP (NiNeoCP) showed broader visible light absorption capacity and better light absorption performance due to the contribution of Ni atom. The blue-shifted Q bands illuminate that the light absorption performance of NeoCP and NiNeoCP varies in different polarity solvents based on the integral equation formalism polarizable continuum model (IEF-PCM) results. These theoretical researches would be conducive to the molecular design of novel multi-band photon absorption porphyrin derivatives. |
| Databáze: | OpenAIRE |
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