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000842076 1001_ $$0P:(DE-Juel1)165797$$aYi, Xiaofeng$$b0
000842076 245__ $$aProbing Frontier Orbital Energies of {Co 9 (P 2 W 15 ) 3 } Polyoxometalate Clusters at Molecule–Metal and Molecule–Water Interfaces
000842076 260__ $$aWashington, DC$$bAmerican Chemical Society$$c2017
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000842076 520__ $$aFunctionalization 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.
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000842076 7001_ $$0P:(DE-HGF)0$$aIzarova, Natalya V.$$b1
000842076 7001_ $$0P:(DE-Juel1)166520$$aStuckart, Maria$$b2
000842076 7001_ $$0P:(DE-HGF)0$$aGuérin, David$$b3
000842076 7001_ $$0P:(DE-Juel1)159335$$aThomas, Louis$$b4
000842076 7001_ $$00000-0002-6857-8752$$aLenfant, Stéphane$$b5
000842076 7001_ $$0P:(DE-HGF)0$$aVuillaume, Dominique$$b6$$eCorresponding author
000842076 7001_ $$0P:(DE-HGF)0$$avan Leusen, Jan$$b7
000842076 7001_ $$0P:(DE-Juel1)165376$$aDuchon, Tomas$$b8$$ufzj
000842076 7001_ $$0P:(DE-Juel1)164137$$aNemšák, Slavomír$$b9
000842076 7001_ $$0P:(DE-HGF)0$$aBourone, Svenja D. M.$$b10
000842076 7001_ $$0P:(DE-Juel1)169869$$aSchmitz, Sebastian$$b11
000842076 7001_ $$0P:(DE-Juel1)130782$$aKögerler, Paul$$b12
000842076 773__ $$0PERI:(DE-600)1472210-0$$a10.1021/jacs.7b07034$$gVol. 139, no. 41, p. 14501 - 14510$$n41$$p14501 - 14510$$tJournal of the American Chemical Society$$v139$$x1520-5126$$y2017
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