Serendipitous formation of oxygen-bridged CuII6M (M = Mn, Co) double cubanes showing electrocatalytic water oxidation.

Hydroxido-bridged CuII6M double-cubane clusters (M = Mn, Co) supported by D-penicillaminedisulfide were unexpectedly formed by treating a D-penicillaminato CuII2PtII2 complex with MBr in water. The clusters displayed heterogeneous electrocatalytic activities for water oxidation dependent on the central M shared by two Cu cubane units.

A chromotropic PtPdCo coordination polymer with dual electrocatalytic activity for water reduction and oxidation.

Here, we present a heterometallic coordination polymer that exhibits heterogeneous electrocatalytic activities for both water reduction and water oxidation. Treatment of the PtII2PdII2 tetranuclear complex [Pd{Pt(NH)(D-pen)}] ([1]; D-Hpen = D-penicillamine) with CoX (X = Cl, Br) provided (PtII2PdII2CoII2) coordination polymers [Co(HO)(1)]X ([2]X), in which the PtII2PdII2 units of [1] are linked by [Co(μ-HO)(HO)] moieties in a 3D network structure. [2]X showed a colour change from orange to dark green upon dehydration, reflecting the geometrical conversion of the Co centres in [Co(μ-HO)(HO)] from an octahedron to a tetrahedron by the removal of aqua ligands.

Dimensional Structures and Electrocatalytic Activities of Platinum(II)-Palladium(II)-Manganese(II) Coordination Polymers Controlled by Chloride versus Bromide.

Here we report the synthesis and structural characterization of heterotrimetallic (PtPdMn) coordination polymers that show different dimensionalities and electrocatalytic activities depending on chloride and bromide employed in the system. The reaction of the PtPd tetranuclear complex [PdPt(NH)(d-pen)] (), bearing free carboxylate groups, with Mn in the presence of chloride produced the (PtPdMn) coordination polymer [MnCl(HO)()]Cl (), in which the PtPd units of are linked by [MnCl(HO)] moieties in a 1:2 ratio to form a 2D sheetlike structure. The corresponding reaction in the presence of bromide also gave the (PtPdMn) coordination polymer [Mn(HO)()]Br (), but adopted a 3D network structure via a 1:1 linkage of the PtPd units with [Mn(HO)] moieties.