Photochromism and Dual-Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch
Dr. Arnaud Parrot
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorAurélie Bernard
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Aurélie Jacquart
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Stefano Artin Serapian
Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology, Avinguda dels Països Catalans 16, 43007 Tarragona, Spain
Search for more papers by this authorProf. Carles Bo
Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology, Avinguda dels Països Catalans 16, 43007 Tarragona, Spain
Department de Química Física i Inorgànica, Universitat Rovira i Virgili, Avda. Marcel.li Domingo s/n., Tarragona, Spain
Search for more papers by this authorDr. Etienne Derat
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Olivier Oms
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorDr. Anne Dolbecq
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorProf. Anna Proust
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Rémi Métivier
PPSM, UMR CNRS 8531, ENS Cachan, 61 av. Président Wilson, 94235 Cachan cedex, France
Search for more papers by this authorCorresponding Author
Prof. Pierre Mialane
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorCorresponding Author
Dr. Guillaume Izzet
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Arnaud Parrot
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorAurélie Bernard
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Aurélie Jacquart
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Stefano Artin Serapian
Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology, Avinguda dels Països Catalans 16, 43007 Tarragona, Spain
Search for more papers by this authorProf. Carles Bo
Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology, Avinguda dels Països Catalans 16, 43007 Tarragona, Spain
Department de Química Física i Inorgànica, Universitat Rovira i Virgili, Avda. Marcel.li Domingo s/n., Tarragona, Spain
Search for more papers by this authorDr. Etienne Derat
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Olivier Oms
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorDr. Anne Dolbecq
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorProf. Anna Proust
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorDr. Rémi Métivier
PPSM, UMR CNRS 8531, ENS Cachan, 61 av. Président Wilson, 94235 Cachan cedex, France
Search for more papers by this authorCorresponding Author
Prof. Pierre Mialane
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, Université Paris Saclay, 45 Avenue des Etats-Unis, F-, 78035 Versailles cedex, France
Search for more papers by this authorCorresponding Author
Dr. Guillaume Izzet
Institut Parisien de Chimie Moléculaire UMR CNRS 8232, Sorbonne Universités, UPMC-Paris06, 4 Place Jussieu, F-, 75005 Paris, France
Search for more papers by this authorGraphical Abstract
Small cause, big effect: A covalent polyoxometalate (POM)–benzospiropyran (BSPR) dyad is an unprecedented example of an organic–inorganic molecular switch that displays a specific fluorescence feature in each photochromic form. The fluorescence of the BSPR unit of the POM-based hybrid is considerably enhanced compared to BSPR reference compounds, which is attributed to a more easily accessible emitting state in the hybrid.
Abstract
The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (λem (closed form)=530 nm, λem (open form)=670 nm) and that the fluorescence of the BSPR unit of the hybrid is considerably enhanced compared to BSPR parent compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), improving the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of the hybrid give an intimate understanding of the conformation adopted by the hybrid and show that the nitroaryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR.
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