TY - JOUR

T1 - The precise modification of a nanoscaled Keplerate-type polyoxometalate with NH2-groups: reactive sites, mechanisms and dye conjugation

AU - Гржегоржевский, Кирилл

AU - Деникаев, Андрей

AU - Морозова, Мария

AU - Пряхина, Виктория

AU - Хайруллина, Евгения Мусаевна

AU - Тумкин, Илья Игоревич

AU - Тания, Ольга

AU - Остроушко, Александр

N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/3/29

Y1 - 2022/3/29

N2 - 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.

AB - 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.

KW - CHEMISTRY

KW - DERIVATIVES

KW - DESTRUCTION

KW - FLUORESCEIN

KW - HYDROLYSIS

KW - MO72FE30

KW - MOLECULES

KW - MOLYBDATE

KW - SPECTROSCOPY

KW - XPS

UR - http://www.scopus.com/inward/record.url?scp=85128763115&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/bbd054a9-be29-34e1-a51d-5dea44f382ec/

U2 - 10.1039/D1QI01454D

DO - 10.1039/D1QI01454D

M3 - Article

VL - 9

SP - 1541

EP - 1555

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 7

ER -