Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes
The structural stability and photoabsorption properties of Ni(II)-based metal-organic complexes with octahedral coordination having different planar ligand ring structures were investigated employing density functional theory (DFT) and its time-dependent extension (TD-DFT) considering the M06 exchan...
| Main Authors: | , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/23/4249 |
| _version_ | 1818278846136320000 |
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| author | Alex-Adrian Farcaș Attila Bende |
| author_facet | Alex-Adrian Farcaș Attila Bende |
| author_sort | Alex-Adrian Farcaș |
| collection | DOAJ |
| description | The structural stability and photoabsorption properties of Ni(II)-based metal-organic complexes with octahedral coordination having different planar ligand ring structures were investigated employing density functional theory (DFT) and its time-dependent extension (TD-DFT) considering the M06 exchange-correlation functional and the Def2-TZVP basis set. The results showed that the molecular composition of different planar cyclic ligand structures had significant influences on the structural stability and photoabsorption properties of metal-organic complexes. Only those planar ligands that contained aromatic rings met the basic criteria (thermal stability, structural reversibility, and appropriate excitation frequency domain) for light-induced excited spin state trapping, but their spin transition efficiencies were very different. While, in all three aromatic cases, the singlet electronic excitations induced charge distribution that could help in the singlet-to-triplet spin transition, and triplet excitations, which could assist in the backward (triplet-to-singlet) spin transition, was found only for one complex. |
| first_indexed | 2024-12-12T23:23:55Z |
| format | Article |
| id | doaj.art-7bc3e2cf43c1469fac3dd36acba48825 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-12T23:23:55Z |
| publishDate | 2019-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-7bc3e2cf43c1469fac3dd36acba488252022-12-22T00:08:11ZengMDPI AGMolecules1420-30492019-11-012423424910.3390/molecules24234249molecules24234249Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand ComplexesAlex-Adrian Farcaș0Attila Bende1National Institute for Research and Development of Isotopic and Molecular Technologies, Donat Street, No. 67-103, Ro-400293 Cluj-Napoca, RomaniaNational Institute for Research and Development of Isotopic and Molecular Technologies, Donat Street, No. 67-103, Ro-400293 Cluj-Napoca, RomaniaThe structural stability and photoabsorption properties of Ni(II)-based metal-organic complexes with octahedral coordination having different planar ligand ring structures were investigated employing density functional theory (DFT) and its time-dependent extension (TD-DFT) considering the M06 exchange-correlation functional and the Def2-TZVP basis set. The results showed that the molecular composition of different planar cyclic ligand structures had significant influences on the structural stability and photoabsorption properties of metal-organic complexes. Only those planar ligands that contained aromatic rings met the basic criteria (thermal stability, structural reversibility, and appropriate excitation frequency domain) for light-induced excited spin state trapping, but their spin transition efficiencies were very different. While, in all three aromatic cases, the singlet electronic excitations induced charge distribution that could help in the singlet-to-triplet spin transition, and triplet excitations, which could assist in the backward (triplet-to-singlet) spin transition, was found only for one complex.https://www.mdpi.com/1420-3049/24/23/4249metal-ligand octahedral coordinationintersystem crossingtd-dftsinglet-triplet spin transitionspin-orbit coupling |
| spellingShingle | Alex-Adrian Farcaș Attila Bende Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes Molecules metal-ligand octahedral coordination intersystem crossing td-dft singlet-triplet spin transition spin-orbit coupling |
| title | Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes |
| title_full | Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes |
| title_fullStr | Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes |
| title_full_unstemmed | Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes |
| title_short | Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes |
| title_sort | improving the light induced spin transition efficiency in ni ii based macrocyclic ligand complexes |
| topic | metal-ligand octahedral coordination intersystem crossing td-dft singlet-triplet spin transition spin-orbit coupling |
| url | https://www.mdpi.com/1420-3049/24/23/4249 |
| work_keys_str_mv | AT alexadrianfarcas improvingthelightinducedspintransitionefficiencyinniiibasedmacrocyclicligandcomplexes AT attilabende improvingthelightinducedspintransitionefficiencyinniiibasedmacrocyclicligandcomplexes |