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      The precise modification of a nanoscaled Keplerate-type polyoxometalate with NH 2-groups: reactive sites, mechanisms and dye conjugation

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          Abstract

          The interaction of alkoxysilanes with nanoscaled giant polyoxoclusters is a challenging route for efficiently building blocks for supramolecular smart design.

          Abstract

          The interaction of alkoxysilanes with nanoscaled giant polyoxoclusters is a challenging route for efficiently building blocks for supramolecular smart design. 3-Aminopropyltrimethoxysilane (APTMS) treatment grafts amino groups onto the surface of the Keplerate {Mo 132} in a controlled manner. By means of XPS and elemental analysis, we studied the influence of the component ratio, the solvent nature, acidity and mixture preparation on the stoichiometry of POM–APTMS conjugates. The reaction mechanism shows the role of {Mo 2} bridging units as reactive sites for APTMS binding. Comprehensive use of IR and Raman spectroscopy shows ring-like siloxane formation above the {Mo 9O 9} pores in {Mo 132}. This approach to the covalent modification of giant polyoxometalates (POM) was successfully applied to the functionalization of another Keplerate {Mo 70Fe 30}. Grafting NH 2 groups opened a way to covalently bind POMs with fluorescein-NHS (FL-NHS), where the strong charge transfer near 526 nm (UV–vis) appears to promote potential photocatalytic activities. Studying the conjugates POM–APTMS with SEM, we discovered a novel nano-object consisting of nanostrips: these are unknown for structures based on nanoclusters from the giant POM family. Thus, these pioneering approaches to giant POM covalent functionalization can be applied to designing templates for supramolecular structures and functional materials.

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          Most cited references73

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          Heteropoly and Isopoly Oxometalates

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            The Infra-red Spectra of Complex Molecules

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              Supramolecular Luminescent Sensors

              There is great need for stand-alone luminescence-based chemosensors that exemplify selectivity, sensitivity, and applicability and that overcome the challenges that arise from complex, real-world media. Discussed herein are recent developments toward these goals in the field of supramolecular luminescent chemosensors, including macrocycles, polymers, and nanomaterials. Specific focus is placed on the development of new macrocycle hosts since 2010, coupled with considerations of the underlying principles of supramolecular chemistry as well as analytes of interest and common luminophores. State-of-the-art developments in the fields of polymer and nanomaterial sensors are also examined, and some remaining unsolved challenges in the area of chemosensors are discussed.
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                Author and article information

                Contributors
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                Journal
                ICFNAW
                Inorganic Chemistry Frontiers
                Inorg. Chem. Front.
                Royal Society of Chemistry (RSC)
                2052-1553
                March 29 2022
                2022
                : 9
                : 7
                : 1541-1555
                Affiliations
                [1 ]Ural Federal University, Institute of Natural Sciences and Mathematics, 19 Mira St., Ekaterinburg, Russia
                [2 ]Institute of Chemistry, St Petersburg State University, St Petersburg, Russia
                Article
                10.1039/D1QI01454D
                44055807-1b57-4cd1-85a6-1d944f573698
                © 2022

                http://rsc.li/journals-terms-of-use

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