caa a22 4500 606174214 CHVBK 20210128100737.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s11244-015-0367-z doi (NATIONALLICENCE)springer-10.1007/s11244-015-0367-z Use of Solvatochromism to Assay Preferential Solvation of a Prototypic Catalytic Site [Elektronische Daten] [Birgit Schwenzer, Lelia Cosimbescu, Vassiliki-Alexandra Glezakou, Abhijeet Karkamkar, Zheming Wang, Robert Weber] The composition of the reaction medium near photoactive catalytic sites can be inferred from the solvatochromism of the absorption and emission spectra of the wetted sites, which depend on the polarizability of the fluid. In brief, solvatochromism measures the interaction of the dipole moments of the ground and excited states with the electric field imposed by the solvent shell: a field, which does not relax on the time scale of the absorption or emission events. To establish the utility of the technique for inorganic catalysts that operate in complex reaction media, such as encountered in the upgrading of biogenic fuels, we have measured the solvatochromism of a common, structural feature of metal oxide catalysts, mono-oxide or dioxide of a transition metal prepared by incorporating the OM or O2M moiety into the framework of a polyhedral oligomeric silsesquioxane (POSS). In toluene, cyclohexene, chloroform and tetrahydrofuran, POSS-ligated oxometalates exhibit strong ligand-to-metal charge-transfer bands in their UV-visible absorption and emission spectra. From the solvatochromism of the chromophores dissolved in toluene-chloroform mixtures we inferred an unexpectedly strong, preferential solvation of the chromophore even when all three components (oxometalate and the two solvents) were highly miscible. Graphical Abstract: Springer Science+Business Media New York (Outside USA), 2015 Luminescence spectroscopy vanadium nationallicence Chromium nationallicence Molybdenum nationallicence Tungsten oxides nationallicence TD-DFT nationallicence Ligand-to-metal charge transfer spectroscopy nationallicence Mesoscale measurements nationallicence Schwenzer Birgit Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut Cosimbescu Lelia Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut Glezakou Vassiliki-Alexandra Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut Karkamkar Abhijeet Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut Wang Zheming Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut Weber Robert Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/4-6(2015-04-01), 258-270 1022-5528 58:4-6<258 2015 58 11244 https://doi.org/10.1007/s11244-015-0367-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-015-0367-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Schwenzer Birgit Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut NATIONALLICENCE 700 1- Cosimbescu Lelia Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut NATIONALLICENCE 700 1- Glezakou Vassiliki-Alexandra Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut NATIONALLICENCE 700 1- Karkamkar Abhijeet Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut NATIONALLICENCE 700 1- Wang Zheming Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut NATIONALLICENCE 700 1- Weber Robert Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 MS-IN K2-12, 99352, Richland, WA, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/4-6(2015-04-01), 258-270 1022-5528 58:4-6<258 2015 58 11244