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Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces

[Image: see text] Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [Co(II)(9)(H(2)O)(6)(OH)(3)(p-RC(6)H(4)As(V)O(3))(2)(α-P(V)(2)W(VI)(15)O(56))(3)](25–) ({Co(9)(P(2)W(15))(3)}, R...

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Autores principales: Yi, Xiaofeng, Izarova, Natalya V., Stuckart, Maria, Guérin, David, Thomas, Louis, Lenfant, Stéphane, Vuillaume, Dominique, van Leusen, Jan, Duchoň, Tomáš, Nemšák, Slavomír, Bourone, Svenja D. M., Schmitz, Sebastian, Kögerler, Paul
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5649444/
https://www.ncbi.nlm.nih.gov/pubmed/28901755
http://dx.doi.org/10.1021/jacs.7b07034
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author Yi, Xiaofeng
Izarova, Natalya V.
Stuckart, Maria
Guérin, David
Thomas, Louis
Lenfant, Stéphane
Vuillaume, Dominique
van Leusen, Jan
Duchoň, Tomáš
Nemšák, Slavomír
Bourone, Svenja D. M.
Schmitz, Sebastian
Kögerler, Paul
author_facet Yi, Xiaofeng
Izarova, Natalya V.
Stuckart, Maria
Guérin, David
Thomas, Louis
Lenfant, Stéphane
Vuillaume, Dominique
van Leusen, Jan
Duchoň, Tomáš
Nemšák, Slavomír
Bourone, Svenja D. M.
Schmitz, Sebastian
Kögerler, Paul
author_sort Yi, Xiaofeng
collection PubMed
description [Image: see text] Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [Co(II)(9)(H(2)O)(6)(OH)(3)(p-RC(6)H(4)As(V)O(3))(2)(α-P(V)(2)W(VI)(15)O(56))(3)](25–) ({Co(9)(P(2)W(15))(3)}, R = H or NH(2)), isolated as Na(25)[Co(9)(OH)(3)(H(2)O)(6)(C(6)H(5)AsO(3))(2)(P(2)W(15)O(56))(3)]·86H(2)O (Na-1; triclinic, P1̅, a = 25.8088(3) Å, b = 25.8336(3) Å, c = 27.1598(3) Å, α = 78.1282(11)°, β = 61.7276(14)°, γ = 60.6220(14)°, V = 13888.9(3) Å(3), Z = 2) and Na(25)[Co(9)(OH)(3)(H(2)O)(6)(H(2)NC(6)H(4)AsO(3))(2)(P(2)W(15)O(56))(3)]·86H(2)O (Na-2; triclinic, P1̅, a = 14.2262(2) Å, b = 24.8597(4) Å, c = 37.9388(4) Å, α = 81.9672(10)°, β = 87.8161(10)°, γ = 76.5409(12)°, V = 12920.6(3) Å(3), Z = 2). The axially oriented para-aminophenyl groups in 2 facilitate the formation of self-assembled monolayers on gold surfaces and thus provide a viable molecular platform for charge transport studies of magnetically functionalized polyoxometalates. The title systems were isolated and characterized in the solid state, in aqueous solutions, and on metal surfaces. Using conducting tip atomic force microscopy, the energies of {Co(9)(P(2)W(15))(3)} frontier molecular orbitals in the surface-bound state were found to directly correlate with cyclic voltammetry data in aqueous solution.
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spelling pubmed-56494442017-10-22 Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces Yi, Xiaofeng Izarova, Natalya V. Stuckart, Maria Guérin, David Thomas, Louis Lenfant, Stéphane Vuillaume, Dominique van Leusen, Jan Duchoň, Tomáš Nemšák, Slavomír Bourone, Svenja D. M. Schmitz, Sebastian Kögerler, Paul J Am Chem Soc [Image: see text] Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [Co(II)(9)(H(2)O)(6)(OH)(3)(p-RC(6)H(4)As(V)O(3))(2)(α-P(V)(2)W(VI)(15)O(56))(3)](25–) ({Co(9)(P(2)W(15))(3)}, R = H or NH(2)), isolated as Na(25)[Co(9)(OH)(3)(H(2)O)(6)(C(6)H(5)AsO(3))(2)(P(2)W(15)O(56))(3)]·86H(2)O (Na-1; triclinic, P1̅, a = 25.8088(3) Å, b = 25.8336(3) Å, c = 27.1598(3) Å, α = 78.1282(11)°, β = 61.7276(14)°, γ = 60.6220(14)°, V = 13888.9(3) Å(3), Z = 2) and Na(25)[Co(9)(OH)(3)(H(2)O)(6)(H(2)NC(6)H(4)AsO(3))(2)(P(2)W(15)O(56))(3)]·86H(2)O (Na-2; triclinic, P1̅, a = 14.2262(2) Å, b = 24.8597(4) Å, c = 37.9388(4) Å, α = 81.9672(10)°, β = 87.8161(10)°, γ = 76.5409(12)°, V = 12920.6(3) Å(3), Z = 2). The axially oriented para-aminophenyl groups in 2 facilitate the formation of self-assembled monolayers on gold surfaces and thus provide a viable molecular platform for charge transport studies of magnetically functionalized polyoxometalates. The title systems were isolated and characterized in the solid state, in aqueous solutions, and on metal surfaces. Using conducting tip atomic force microscopy, the energies of {Co(9)(P(2)W(15))(3)} frontier molecular orbitals in the surface-bound state were found to directly correlate with cyclic voltammetry data in aqueous solution. American Chemical Society 2017-09-13 2017-10-18 /pmc/articles/PMC5649444/ /pubmed/28901755 http://dx.doi.org/10.1021/jacs.7b07034 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Yi, Xiaofeng
Izarova, Natalya V.
Stuckart, Maria
Guérin, David
Thomas, Louis
Lenfant, Stéphane
Vuillaume, Dominique
van Leusen, Jan
Duchoň, Tomáš
Nemšák, Slavomír
Bourone, Svenja D. M.
Schmitz, Sebastian
Kögerler, Paul
Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title_full Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title_fullStr Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title_full_unstemmed Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title_short Probing Frontier Orbital Energies of {Co(9)(P(2)W(15))(3)} Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
title_sort probing frontier orbital energies of {co(9)(p(2)w(15))(3)} polyoxometalate clusters at molecule–metal and molecule–water interfaces
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5649444/
https://www.ncbi.nlm.nih.gov/pubmed/28901755
http://dx.doi.org/10.1021/jacs.7b07034
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