A Basket‐Like [Sr⊂P 6 Mo V 4 Mo VI 14 O 73 ] 10– Polyoxoanion Modified with {Cu(phen)(H 2 O) x } ( x = 1–3) Fragments: Synthesis, Structure, Magnetic, and Electrochemical Properties

Hydrothermal reaction of a mixture of Na 2 MoO 4 · 2H 2 O, H 3 PO 4 , CuCl 2 · 2H 2 O, o ‐phenanthroline, and SrCl 2 in water leads to the isolation of a basket‐like mixed‐valent polymolybdophosphate hybrid compound, [Cu(phen)(H 2 O) 3 ][{Cu(phen)(H 2 O) 2 }{Cu(phen)(H 2 O)} 3 {Sr⊂P 6 Mo 4 V Mo 14 VI O 73 }] · 3H 2 O 1 , which crystallizes in the space group P $\bar {1}$ with a = 13.778(3) Å, b = 19.267(4) Å, c = 24.168(5) Å, α = 110.64(3)°, β = 90.31(3)°, γ = 110.02(3)°, V = 5582.8(2) Å 3 , Z = 2. Single‐crystal X‐ray diffraction analysis shows that the four‐electron‐reduced basket‐like polyoxoanion [Sr⊂P 6 Mo 4 V Mo 14 VI O 73 ] 10– contains a new tetravacant γ‐Dawson‐type unit and a “handle”‐shaped {P 4 Mo 4 } segment, which are highly modified with {Cu(phen)(H 2 O) x } ( x = 1–3) fragments. Electrochemical analysis shows that 1 ‐modified carbon paste electrode (CPE) displays good electrocatalytic activity to reduce hydrogen peroxide. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)