Search

Nanoscale {Nb68O200} cages have been successfully employed as flexible and stable secondary building units to combine with bridging copper–amine complexes to construct two proton conductive polyoxoniobate frameworks, demonstrating a promising strategy for making new porous materials. [ABSTRACT FROM AUTHOR]

Compounds with redox activities have appealing applications in catalytic, electronic and magnetic properties, but the redox inert of polyoxoniobates (PONbs) significantly limits their applications for a long time. In this work, we are able to integrate organophosphate and lanthanide cluster into PONb to create the first family of inorganic-organic hybrid organophosphate-Ln-PONb composite clusters. These novel species not only present the first family of redox active PONbs that can be reduced to form long-lived "heteropoly blues" under ambient conditions, but also a new photochromic system. More importantly, the analyses of the electronic configurations and photochromic properties for a series of designed proof-of-concept PONbs models allow us to discover a D-f-A electron transfer mechanism, that is, photoinduced electron is transferred from a photosensitive organophosphate electron donor (D) to the Nb V electron acceptor (A) through the unoccupied 4 f-orbitals of Ln (f). This work paves the way for developing diverse PONb-based redox materials and expanding the possibility of the applications of PONbs in the redox chemistry., (© 2023 Wiley-VCH GmbH.)

A rare 3D Indium-containing polyoxoniobate framework {H 9 [Cu(en) 2 (H 2 O) 2 ][Cu(en) 2 ] 12 [In(en)] 5 [Nb 23 -O 65 (OH) 3 (H 2 O) 2 ]{Nb 24 O 67 (OH) 2 (H 2 O) 3 ] 2 }·68H 2 O( 1 ), based on the In-containing polyoxoniobate cluster, {[In(en)] 5 [Nb 23 O 65 (OH) 3 (H 2 O) 2 ][Nb 24 O 67 (OH) 2 (H 2 O) 3 ] 2 } 35- ({In 5 Nb 71 }) and [Cu(en) 2 ] 2+ linkers has been successfully synthesized. The nest-like cluster {In 5 Nb 71 } is constructed from one brand-new V-shaped {Nb 23 O 70 }, two triangle-shaped {Nb 24 O 72 } and five [In(en)] 3+ . The [In(en)] fragments link {Nb 24 O 72 } and {Nb 23 O 70 } units into unique {In 5 Nb 71 } n helical pillars. The copper-amine complexes connect the {In 5 Nb 71 } n helical pillars into a three-dimensional (3D) inorganic-organic hybrid In-Cu-containing framework. This material also exhibits good ionic conductivity and vapor adsorption capacity properties.

Nanoscale {Nb68O200} cages have been successfully employed as flexible and stable secondary building units to combine with bridging copper-amine complexes to construct two proton conductive polyoxoniobate frameworks, demonstrating a promising strategy for making new porous materials.