A trigonal prismatic Cu6L3 coordination cage has been assembled from Cu(I) and semi‐rigid bipyrazolyl ligand. The X‐ray crystallography demonstrates that the cage has a cavity and can encapsulate the toluene as a guest, exhibiting thermochromism phenomenon. Empty cage can be obtained by expulsion of the guest through single crystal to single crystal transformation. After removed the guest, the empty cage shows a blue‐shifted emission (580 nm), in comparison to its parent cage (615 nm). The empty cage could further serve as a host to encapsulate other aromatic molecules (e. g. mesitylene), which shows new emission band. The trigonal prismatic Cu6L3 coordination cage provides a platform to make advanced luminescent materials.

No abstract

Bipodal diacylthioureas [MesC(O)NHC(S)NH]2R (R = C6H4‐1,2 (L1, 1), C6H4‐1,4 (L2, 2)) were synthesized, and their complexation reactions with equimolar Cu(I) halides CuX (X = Cl, Br, ) were investigated. The obtained ligands L1–2 and the resultant Cu(I) complexes (3–8) were characterized by FT‐IR, 1H NMR, 13C NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The complexation of L1 with CuX gave three different 1D polymers: the infinite single chain (L1CuCl)n (3), edge‐shared double‐ring chain {[(µ‐L1)CuBr]2}n (4), and vertex‐shared double‐ring chain {[L1Cu(µ‐I)]2}n (5). Similarly, but more pronounced, the treatment of L2 with CuX resulted in the formation of 1D edge‐shared double‐ring chain {[(µ‐L2)CuCl]2}n (6), 0D discrete dinuclear metallamacrocyclic ring (L2CuBr)2 (7), and 3D network polymer [L2Cu(µ‐I)]n (8), respectively. The structural diversity may be related to the suitable spacer, flexible C=S directionality and binding roles of halide anions and sulfur donors. Among Cu(I) complexes (3–8) as prepared, both chloride (in 3 and 6) and bromide anions (in 4 and 7) acted as terminal ligands, while the iodide anions (in 5 and 8) served as bridging ligand. In contrast, only in edge‐shared double‐ring chains (4 and 6) it was found that the sulfur donors (one of two in each Ln) played as the bridging ligand.