View in EDS

Azobenzene-derived tris-β-diketonate lanthanide complexes: reversible trans-to-cis photoisomerization in solution and solid state.

Saved in:
Bibliographic Details
Title: Azobenzene-derived tris-β-diketonate lanthanide complexes: reversible trans-to-cis photoisomerization in solution and solid state.
Authors: Lin, Li-Rong1, Wang, Xuan1, Wei, Gao-Ning1, Tang, Hui-Hui1, Zhang, Hui1, Ma, Li-Hua2
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 10/14/2016, Vol. 45 Issue 38, p14954-14964. 11p.
Subjects: Azobenzene derivatives, Photoisomerization, Complex compounds, Ketones, Rare earth metals, Excitation energy (In situ microanalysis), Density functional theory
Abstract: Novel azobenzene-derived β-diketonates (4,4,5,5,6,6,6-heptafluoro-1-azobenzene-1,3-hexanedione (LA), 4,4,5,5,6,6,6-heptafluoro-1-(4-dimethylamino)azobenzene-1,3-hexanedione (LB)) were designed and their complexes with lanthanide cations (La3+, Eu3+, Gd3+, Yb3+) were prepared and characterized by 1H NMR, FT-IR, and elemental analysis. Three of the complexes were crystallized successfully and identified by X-ray diffraction. It was significant to find that LA showed remarkably reversible trans-to-cis isomerization properties, however, LB, bearing an electron donor compared with LA, slowed down the isomerization to an extent. The presence of Ln(iii) enhanced the reversible trans-to-cis isomerization properties of both LA and LB a little upon photoirradiation in organic solvents, and amazingly increased the fatigue resistance. In addition, the complexes doped in polymethyl methacrylate (PMMA) films produced a similar phenomenon as well as when in solution. Theoretical calculations based on time dependent density functional theory (TD-DFT) were performed for geometry optimization and to determine the excitation energies of LA and LB to gain further insight into the electronic structure of the complexes, and the data were consistent with the experimental results. The excellent reversible photoisomerization properties of the newly designed Ln(iii) complexes can offer important advantages that will help with the further study of these materials to reach their full potential in applications such as molecular switching devices. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
Description
Abstract:Novel azobenzene-derived β-diketonates (4,4,5,5,6,6,6-heptafluoro-1-azobenzene-1,3-hexanedione (LA), 4,4,5,5,6,6,6-heptafluoro-1-(4-dimethylamino)azobenzene-1,3-hexanedione (LB)) were designed and their complexes with lanthanide cations (La3+, Eu3+, Gd3+, Yb3+) were prepared and characterized by 1H NMR, FT-IR, and elemental analysis. Three of the complexes were crystallized successfully and identified by X-ray diffraction. It was significant to find that LA showed remarkably reversible trans-to-cis isomerization properties, however, LB, bearing an electron donor compared with LA, slowed down the isomerization to an extent. The presence of Ln(iii) enhanced the reversible trans-to-cis isomerization properties of both LA and LB a little upon photoirradiation in organic solvents, and amazingly increased the fatigue resistance. In addition, the complexes doped in polymethyl methacrylate (PMMA) films produced a similar phenomenon as well as when in solution. Theoretical calculations based on time dependent density functional theory (TD-DFT) were performed for geometry optimization and to determine the excitation energies of LA and LB to gain further insight into the electronic structure of the complexes, and the data were consistent with the experimental results. The excellent reversible photoisomerization properties of the newly designed Ln(iii) complexes can offer important advantages that will help with the further study of these materials to reach their full potential in applications such as molecular switching devices. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/c6dt01310d