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 promissing...
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.
A series of 3d-4f heterometallic cluster incorporated polyoxoniobates (PONbs) with different magnetic properties were first made and characterized. This work not only provides a promising strategy to make new heterometallic...
A rare
3D Indium-containing polyoxoniobate framework {H9[Cu(en)2(H2O)2][Cu(en)2]12[In(en)]5[Nb23–O65(OH)3(H2O)2]{Nb24O67(OH)2(H2O)3]2}·68H2O(1), based on the In-containing
polyoxoniobate cluster, {[In(en)]5[Nb23O65(OH)3(H2O)2][Nb24O67(OH)2(H2O)3]2}35– ({In5Nb71}) and [Cu(en)2]2+ linkers has been successfully synthesized.
The nest-like cluster {In5Nb71} is constructed
from one brand-new V-shaped {Nb23O70}, two triangle-shaped
{Nb24O72} and five [In(en)]3+. The
[In(en)] fragments link {Nb24O72} and {Nb23O70} units into unique {In5Nb71}
n
helical pillars. The copper-amine
complexes connect the {In5Nb71}
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.
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