TY  - JOUR
AU  - Yi, Xiaofeng
AU  - Izarova, Natalya V.
AU  - Stuckart, Maria
AU  - Guérin, David
AU  - Thomas, Louis
AU  - Lenfant, Stéphane
AU  - Vuillaume, Dominique
AU  - van Leusen, Jan
AU  - Duchon, Tomas
AU  - Nemšák, Slavomír
AU  - Bourone, Svenja D. M.
AU  - Schmitz, Sebastian
AU  - Kögerler, Paul
TI  - Probing Frontier Orbital Energies of {Co 9 (P 2 W 15 ) 3 } Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
JO  - Journal of the American Chemical Society
VL  - 139
IS  - 41
SN  - 1520-5126
CY  - Washington, DC
PB  - American Chemical Society
M1  - FZJ-2018-00357
SP  - 14501 - 14510
PY  - 2017
AB  - Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [CoII9(H2O)6(OH)3(p-RC6H4AsVO3)2(α-PV2WVI15O56)3]25– ({Co9(P2W15)3}, R = H or NH2), isolated as Na25[Co9(OH)3(H2O)6(C6H5AsO3)2(P2W15O56)3]·86H2O (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) Å3, Z = 2) and Na25[Co9(OH)3(H2O)6(H2NC6H4AsO3)2(P2W15O56)3]·86H2O (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) Å3, 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 {Co9(P2W15)3} frontier molecular orbitals in the surface-bound state were found to directly correlate with cyclic voltammetry data in aqueous solution.
LB  - PUB:(DE-HGF)16
C6  - pmid:28901755
UR  - <Go to ISI:>//WOS:000413503300029
DO  - DOI:10.1021/jacs.7b07034
UR  - https://juser.fz-juelich.de/record/842076
ER  -