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)<sub>3</sub>(dppz)⁺ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observ...
Guardado en:
| Autores principales: | , , , , , , |
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| Formato: | Articulo |
| Lenguaje: | Inglés |
| Publicado: |
2018
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| Materias: | |
| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/105765 https://www.sciencedirect.com/science/article/abs/pii/S1010603017313989 |
| Aporte de: |
| Sumario: | A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)<sub>3</sub>(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/HClO<sub>4</sub>. 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 <sup>3</sup>IL(ππ*), <sup>3</sup>MLCT(phz) and the 3MLCT(phen) states. |
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