Two hybrids, [BMIP][Pb 2 Cl 6 ] (1) and [BMIP] [Pb 1.5 Cl 5 ]· H 2 O (2) {BMIP 2+ = 1,3-bis(1-methylimidazolium)propane}, are achieved by mutual diffusion of inorganic and organic components in anhydrous DMF and DMF with a trace amount of water (the trace amount of water originates from MnCl 2 ·4H 2 O), respectively. Single-crystal X-ray diffraction data are collected for 1 in 300-100 K and 2 in 370-100 K, revealing that 1 and 2 crystallize in monoclinic space group P2 1 /c and triclinic space group P1, respectively. Crystal 1 contains [Pb 4 Cl 12 ] ∞ twin chains, rarely reported, constructed from edge-sharing PbCl 6 octahedra, and dications surround the [Pb 4 Cl 12 ] ∞ twin chains. Crystal 2 includes [Pb 3 Cl 10 ] ∞ single chains, comprised of distorted PbCl 6[a]

Under solvothermal conditions, a robust Pb2+-based coordination polymer (CP), [Pb(TDC)]n (1), where H2TDC is thiophenedicarboxylic acid, has been achieved. Structural analysis reveals that 1 crystallizes in the monoclinic space group C2/c, where the Pb2+ ions show quadrangular prism coordination geometry. CP 1 represents a 3D coordination network based on a TDC2- ligand as bridges and quadrangular prismatic PbO8 units as nodes, among which the PbO8 units are extended through edge-sharing to form a 2D layer in the bc plane. Interestingly, CP 1 emitted intense and long-lived orange phosphorescence in the solid state at room temperature, with a quantum yield of 6.7% and a phosphorescence lifetime of 1.78 ms. A fine structure is clearly observed in the phosphorescence emission spectra at temperatures below 55 K. The emission mainly arose from the electron transition within the π-type orbitals of the TDC2- ligand. This study gives a fresh impetus to achieve CP-based long-lived phosphorescent materials under ambient conditions.

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