First published as an Advance Article on the webTwo photoluminescent two-and three-dimensional coordination polymers consisting of Zn 4 O [or Zn 4 (OH) 2 ] cores, dicarboxylate (isophthalate or fumarate) and 4,4A-bipyridine ligands as building blocks have been hydrothermally synthesized and structurally characterized.The construction of supramolecular architectures are currently of great interest owing to their intriguing network topologies and potential functions as new classes of materials. 1 Polynuclear d 10 metal (Cu I , Ag I , Au I , Zn II or Cd II ) complexes have been found to exhibit intriguing structural and photoluminescent properties. 2-5 We have been pursuing synthetic strategies for non-interpenetrating open frameworks with variable cavities or channels using simple units as building blocks. 6 We now extend to work towards extended networks based on metal clusters as building blocks, and report here the preparation and crystal structures of two novel coordination polymers constructed by zinc cluster cores, 4,4A-bipyridine (4,4A-bpy) and dicarboxylate ligands, namely [Zn 4 O(ip) 3 (4,4A-bpy)] (ip = isophthalate) 1 and [Zn 4 (OH) 2 (fa) 3 (4,4A-bpy) 2 ] (fa = fumarate) 2.

White light: [{Au(L)}3] (L=3‐(2‐thienyl)pyrazolate) gives dual emission, one from an organic chromophore the other from aurophilic stacking interactions. The resulting blue–green and orange–red emissions can be tuned to approach white‐light by modulating the aggregation behavior of the cluster.

We observed an unusual reversible aggregation process showing stimuli-responsive structural dynamics and optical changes attributed to the formation of a sandwich-like Au3-Ag-Au3 cluster, which can be synthesized through both solution and mechanochemical methods. Unlike many other heteronuclear gold-silver clusters, the affinity of two cyclic Au3 complexes and a Ag(I) ion is solely bound by ligand unsupported Au-Ag bonding. The assembly/disassembly behavior, further forming nanoaggregates, is controllable by adjusting the concentration of the solution. In the solid state, the insertion of Ag(I) ion can be implemented through a mechanochemical approach, accompanied by visual color changes and reversible luminochromism. Furthermore, an uncommon solid-liquid extraction is demonstrated, showing the uniqueness of this labile Au-Ag metallophilicity and hinting at the possibility of manipulating a bonding process through a heterogeneous route.