Photochemical properties of a Re(I) polymer containing dppz in its structure. An interplay between dark and bright states of dppz
A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)3(dppz)+ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observed by AFM and TEM in ca...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2018 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/99692 |
| Acceso en línea: | http://hdl.handle.net/11336/99692 |
| Access Level: | acceso abierto |
| Palabra clave: | AFM MORPHOLOGY PHOTOCHEMISTRY RHENIUM COMPLEXES TD-DFT TEM https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)3(dppz)+ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observed by AFM and TEM in cast films of P4VP-Re(dppz) in solvents of different polarity and solvent/acid mixtures. Several conformations of a model monomer of P4VP-Re(dppz) were studied by TD-DFT to ascertain the effect of protonation over the molecular structure as well as over the absorption spectroscopy of P4VP-Re(dppz). P4VP-Re(dppz) excited states and their redox reactivity towards the sacrificial reductant TEOA were studied by flash photolysis experiments either in DMF and in DMF/HClO4. Those experiments were compared to the ones derived from thermal reactions of P4VP-Re(dppz) with solvated electrons in pulse radiolysis experiments. All the photophysical and photochemical properties studied were rationalized in terms of an interplay between 3IL(ππ*), 3MLCT(phz) and the 3MLCT(phen) states. |
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