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Diphenyliodonium cations were firstly introduced into halobismuthate system to synthesize two new hybrids, i. e. (DPI)4(Bi2I10) (1) and (DPI)4(Bi2Br10)·H2O (2) (DPI = diphenyliodonium). Two hybrids are isostructures containing (Bi2X10)4- halobismuthate dimmers and diphenyliodonium cations. Hypervalent I(III)⋯X interactions and C H⋯X (X I, Br) hydrogen bonds stabilize the structures and contribute to the structural extending from 0-D clusters to 2-D layer/1-D chain. The broader absorption spectra and lower energy gap of 1 were led by strong I⋯I interactions. Two compounds display thermochromism behaviors, whose mechanisms were verified by theoretical calculations.

A 3-D supramolecular hybrid {[La(EPC) 3 (H 2 O) 3 ] 2 (Pb 6 I 18 )} n (EPC + = N-ethyl-pyridium-4-carboxylate) (1) has been structurally determined, which assume significance for its incorporating lanthanide metal-carboxylic coordination polycation into polymeric iodoplumbate to get heterometallics. 1 consists of 1-D ( Pb 6 I 18 ) n 6n- zigzag-like anion chains with lanthanide metalcarboxylic [ La ( EPC ) 3 ( H 2 O ) 3 ] n 3n + polycations, which arrange in a criss-cross configuration. C–H⋯I and C–H⋯O hydrogen bonds among inorganic anions and polycations contribute to the formation of a 3-D supramolecular framework. Moreover, the framework displays an absorption edge at 2.46 eV which is comparable to PbI 2 ’s absorption edge.

Three new haloplumbates(II)/aromatic N-heterocyclic organic hybrids, [(nmp)(PbI3)]n (nmp = N-methylpyrazine)(1), [(dhpp)(Pb2Cl6)]n (dhpp = 6,12-dihydrodipyrido[1,2-a:1′,2′-d] pyrazinium)(2), [(dedp)3(Pb6I18)]n (dedp = N,N′-diethyl-4,4′-dipyridinium)(3) have been synthesized and structurally determined. These polymeric haloplumbates exhibit different model type structures, including one-dimensional linear chain (for 1), ribbonlike arrangement based on face- and edge-sharing PbXn tetragonal pyramids or octahedra (for 2 and 3), and N-heterocyclic organic cations weakly interact with inorganic haloplumbates to present 3-D supramolecular networks. Three compounds posses semiconducting properties with Eg ranging among 2.07–2.71 eV. Photoluminescence and third-order nonlinear optical (NLO) activity of 3 were also discussed.

A hybrid iodoargentate [(APHEN-H) 2 (Ag 4 I 6 )] n ( 1 ) (APHEN = 5-amino-1,10-phenanthroline) has been obtained by the routine synthetic reaction and structurally determined. In 1 , a ( Ag 4 I 6 ) n 2 - chain was defined by edge-sharing of Ag 4 I 6 units, and its quasi-three-dimensional hybrid structure was constructed from π–π interactions and C H⋯I hydrogen bonds. Experimental band gap of about 2.30 eV indicates its semiconductor nature. Strong luminescence can be detected in the title compound, which has been assigned by theoretical calculation with DFT method.

Phenanthroline derivative, 4,5-diazafluoren-9-one(dafone), was introduced into lead iodine hybrid to synthesize a new hybrid [Pb2I4(dafone)2]n (1), in which each lead atom adopts a distorted octahedral coordination and presents a one-dimensional polymer by edge-sharing mode. Due to the presence of O acceptor in dafone, C–H⋯O hydrogen bonds can be observed and contribute to the formation of 2-D layer. Experimental and theoretical optical property investigation indicate that 1 possesses semiconductor property. Specially, DFT calculation suggests that 1 displays a reduced band gap (1.36 eV), which is assigned to a more dispersed LUMO band compared with [Pb2I4(phen)2]n and [Pb2I4(bipy)2]n.

Dark-red block-shaped crystals of the ionic compound (ipq)4[(Cu2I6)·2I2] (1) (ipq+ = N-(isopentyl)-quinolinium) were obtained by the reaction of ibq·I, CuI with I2 in polar solvent DMF. Compound 1 crystallizes in triclinic system [space group P 1 ¯ Z = 2, a = 10.4236(8) A, b = 12.1950(9) A, c = 15.6214(10) A, α = 95.879(2)°, β = 102.174(2)° and γ = 113.757(2)°]. As indicated by structural analysis, 1 is constituted by ipq+ cations, [Cu2I6]4− anions and molecular iodine [dI−I = 2.8499(5) A]. In 1, dimer Cu2I64− anion is composed by two edge-sharing CuI4 tetrahedra. Cu2I64− anions interact with I2 via strong I⋯I interaction to give [(Cu2I6)·2I2]4− clusters. Furthermore, electrostatic interactions between organic cations and inorganic clusters could be observed and contribute to the crystal packing. Finally, quantum chemistry calculation with DFT method was carried out to reveal the electronic structure of 1.