Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 14, Pages 5367-5375Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja4131615
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Funding
- European Research Council (ERC)
- Region des Pays de la Loire [Marches 278845]
- Fondazione Cariplo [2010-0525]
- MIUR (FIRB) [RBPR05JH2P]
- CNR
- BRESMAT network
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Novel photochromic dithienylethene-based platinum(II) complexes.((CNN)-N-boolean AND-N-boolean AND)Pt(C C-DTE-C6H4-D) (((CNN)-N-boolean AND-N-boolean AND) = 4,4'-di(n-hexyl)-6-phenyl-2,2'-bipyridine; D = H, NMe2) were prepared and characterized. Their excellent photochromic properties allow the photoinduced switching of their second-order nonlinear optical properties in solution, as measured by the EFISH technique, due to formation of an extended pi-conjugated ligand upon suitable electromagnetic radiation. Insights into the electronic structures of the complexes and the nature of their excited states have been obtained by DFT and TD-DFT calculations. These novel Pt(II) complexes were nanoorganized in polymer films which were poled, affording new materials characterized by a good second-order NLO response that can be easily switched, with an excellent NLO contrast. To the best of our knowledge, our compounds allowed designing the very first examples of switchable NLO polymer films based on metal complexes.
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