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New hybrids constructed from diphenyliodonium and metal thiocyanates have been prepared, and their photo-induced structural transformations and corresponding color/fluorescence/magnetism variations have been investigated.

The unique luminescence mechano/thermochromism of a diphosphonium/iodocuprate(i) hybrid is led by the mechanically induced adjustments in cuprophilic interactions and bent P–O–P backbone upon heating.

The dimensionality of uranyl–organic frameworks can range from a neutral 1-D chain or a 2-D planar non-interpenetrated honeycomb layer to twofold interpenetrated (6,3) sheets, and complete or part quenching of uranyl luminescence can be achieved.

The combination of hexacyanoferrate anions with protonated N,N′-dipyridyl-naphthalene diimide tectons resulted in a novel cuboid 3-D H-bonded anion-coordinated framework. Induced by anion–π interactions, such a unique framework is further catenated into an unprecedented five-fold interpenetrated D–A hybrid heterostructure with 1-D hexacyanoferrate polyanions and naphthalene diimide aggregates as electron donors and acceptors, respectively. The photophysical and photochemical properties have also been discussed.

The mono-substituted bipyridinium derivative 1-(3-carboxybenzyl)-4,4′-bipyridinium (cbpy) and polyiodide were adopted to construct two new lead-carboxylate hybrids: [Pb(cbpy)I3·I3]n (1) and {[Pb(cbpy)2](I3)4·I2}n (2), in which interesting halogen bonds were detected. Specifically, the hybrids demonstrate efficient photocatalytic degradation of organic dyes and excellent photocurrent response, and the mechanisms of degradation have been discussed and verified using theoretical calculations.

The first transition-metal-bridged polyniobotungstate-based 3D framework has been hydrothermally synthesized, which is constructed from bi-[CuII(en)2(H2O)]-decorating [Nb3W3O19]5− polyoxoanions linked together by CuI ions. Interestingly, the 3D polyniobotungstate framework can undergo a solid–liquid reaction with KI solution to generate a 1D copper halide of [Cu(en)2][CuI2]2 in a single-crystal-to-single-crystal process.

A 2-D metal–organic hybrid framework, [(Nd2DMF12IN2)(Pb8I20)]n (HIN = isonicotinic acid) was structurally determined, which was constructed from a lanthanide metal complex and 1-D lead–iodine polymersvia a HIN ligand with mixed coordination sites.

We extend our efforts to investigate the influence of ligand spacers on iodoargentate hybrids templated by cationic SDAs [structure-directing agents, BPB2+ (1,4-bis(pyridinium)butane), BPO2+ (1,8-bis(pyridinium)octane)] possessing both rigidity and flexibility and two iodoargentate hybrids [(BPB)(Ag5I7)]n (1), [(BPO)(Ag5I7)]n (2) have been synthesized in polar organic solvents. 1 exhibits a 3-D network with BPB2+ cations trapped in the 3-D (Ag5I7)n2− cavities and 2 contains one-dimensional infinite polymeric anions accompanied by discrete SDA cations. Interestingly, judging from structural analysis and DFT calculations, we find that the rigidity/flexibility competition will achieve a balance when the ligand spacer n is 4, where the most versatile structure and stable confirmation can be presented. Their adsorption and fluorescent spectra are also discussed.

Three lead iodide–organic coordination polymers with different substituents on 1,10-phenanthroline, [(5-S-phen)PbI2]n (S = –NO2(1), –Cl(2) and –NH2(3)) have been synthesized in polar organic solvent under nearly the same conditions. 1 and 2 are structurally similar to each other, and exhibit 3-D networks based on inter-layer hydrogen bond interactions. 3 also gives 3-D arrangement viahydrogen bonds among 1-D chains. To our interest, we found that the ligand's electronic nature is the dominant factor in the dimension extending behavior; EWGs (electron-withdrawing group) on the phenanthroline ring will lead to larger electron mobility in a coordinated skeleton, but EDGs (electron-donating group) will give a smaller charge carrier mobility. Consequently, from EWGs to EDGs, an enlarged band gap can be observed. Their luminescences were also discussed.

A 3-D organic–inorganic hybrid heterobridging copper(I) polymer {[Cu2I2(Hgtsc)]·2DMF}n (1A) (Hgtsc=glyoxal-dithiosemicarbazone) with an unusual bridging mode involving iodine and sulfur atoms has been structurally determined, which was constructed from supramolecular interactions between 2-D hybrid layers [Cu2I2(Hgtsc)]n and solvent molecules (DMF). Strong luminescence can be detected and interestingly, thermochromic behavior can be observed.

The introduction of series of organic conjugated ligands into the Pb/I system leads to the formation of three lead(II)/iodine polymers [Pb2I4(dpdo)]n (1) (dpdo = 4,4′-dipyrdiyl-N,N′-dioxide), [PbI2(bipyO2)]n (2) (bipyO2 = 2,2′-dipyrdiyl- N,N′-dioxide) and {[PbI(Dhydql)]∙DMF}n (3) (Dhydql = deprotonated 8-hydroxyquinoline). In 1 and 2, both the organic and inorganic ligands are neutral. But the organic moiety in 3 is a conjugated negative ion and the inorganic component presents a 2-D layer arrangement. The organic ligands in this work serve as bridges to link the inorganic chain or layer to heighten the structural dimension. As expected, based on the bridge nature of an organic ligand, 1 features a 2-D arrangement of a staircase-like lattice sheet [Pb2I4(dpdo)]n, 2 exhibits a 1-D chain [PbI2(bipyO2)]n consisting of unprecedented twisted boat from seven-membered rings, and 3 presents a host–guest structure with DMF as guest molecules which are embedded in between adjoining inorganic–organic components. Furthermore, the compounds were further characterized with fluorescence, UV-vis spectra and third-order non-liner optical (NLO) properties.