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Optical, third order non-linear optical and electrochemical properties of dipolar, centrosymmetric and C2v organoimido polyoxometalate derivatives
- Publication Year :
- 2021
-
Abstract
- A family comprising seven arylimido-polyoxometalate (POM) hybrid chromophores (three of which are new), with linear dipolar, C2v and linear centrosymmetric geometries have been synthesised and studied by electronic absorption spectroscopy, electrochemistry, Z-scans (two photon absorption, TPA) and computation (DFT/TD-DFT). These reveal that POM acceptor units are an effective basis for TPA materials: the centrosymmetric bis-POM chromophores produce significant cross sections (δ up to 82 GM) from a single aryl bridge, a similar performance to larger dipolar π-systems combining carbazole or diphenylamino donors with the imido-POM acceptor. DFT/TD-DFT calculations indicate strong communication between POM and organic components is responsible for the linear and non-linear optical behaviour of these compounds, while electrochemical measurements reveal class II mixed valence behaviour resulting from an interplay of through-bond and through-space effects.
- Subjects :
- Valence (chemistry)
Materials science
Absorption spectroscopy
Carbazole
Aryl
General Physics and Astronomy
02 engineering and technology
Chromophore
010402 general chemistry
021001 nanoscience & nanotechnology
01 natural sciences
Acceptor
Two-photon absorption
0104 chemical sciences
chemistry.chemical_compound
Crystallography
chemistry
Polyoxometalate
Physical and Theoretical Chemistry
0210 nano-technology
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....096c5207f9e20a6699b183b89b79e1c9