A new halocadmium/methyl viologen hybrid (MV)4(Cd2I6)(Cd2I7)2 (1) (MV2+ = methyl viologen) has been structurally determined. In 1, two kinds of dimeric halocadmium clusters constructed from edge/vertex-sharing CdI4 tetrahedra respectively, i.e., Cd2I62− and Cd2I7− dimmers were observed, which were templated by methyl viologen cation (MV2+). A highly interesting feature of 1 is the presence of mixed type dimeric halocadmium clusters in one crystal lattice templated by one kind of cation. 1 displays photoluminescences, and its thermochromism behavior is observed, whose mechanism was verified by theoretical calculations.

A mild and efficient copper-mediated trifluoromethylthiolation of acid chlorides using (bpy)CuSCF3 has been developed. A wide range of S-trifluoromethyl esters were synthesized in good to excellent yields and various functional groups, including cyano, ether, ester, halide, nitro, et al. were well tolerated.

Four uranium(VI)-polycarboxylates frameworks with honeycomb (6,3) nets have been assembled from solvothermal systems, which contain different guest molecules (transition metal complexes and methyl viologen). These compounds exhibit photocatalytic activities for the degradation of rhodamine B. Interestingly, the methyl viologen-containing one possesses the highest efficiency, which can be attributed to the electron acceptor nature of methyl viologen for the stabilization of active peroxide anions.

Alkali metals were introduced into heavy main-group iodometallates to get two new IA/IVAheterometallic frameworks [PbI3K(pdon)(H2O)2]n (1) and {[Pb3I9K2(pdon)2(H3O)] ⋅H2O}n (2) (pdon =1,10-phenanthroline-5,6-dione), which were obtained as single phases by hydrothermal method at different pH values. Compounds 1 and 2 are three-dimensional heterometallic frameworks constructed from the linkage of pdon ligand between iodometallate chains and potassium oxides/iodide clusters. Specially, these two heterometallic frameworks exhibit broadened absorption bands at 700 and 750 nm compared with those of bulk PbI2 and pdon ligand. The band gap of 2 is wider than that of 1, which is due to the absence of π⋯π interaction in 2. Their thermal stabilities are also discussed.

Two new methyl viologen halocadmium charge-transfer salts with isostructures, [(MV)(CdI4)]2·3H2O (1) and (MV)(CdI4)·H2O (2) (MV = methyl viologen, i.e., 1,1′-dimethyl-4,4′-bipyridinium), have been structurally determined. 1 and 2 consist of CdI42− clusters, MV2+ dications, lattice waters with isostructures, and C–H···I hydrogen bonds are presented in 1 but absent in 2, furthermore, their relative stabilities based on were investigated by DFT calculations. Both compounds display photoluminescences in the visible region under visible-light excitations, and their thermochromism effects are observed. But their photoluminescence and thermochromic behaviors differ greatly with the presence or absence of hydrogen bonds. Moreover, their absorption spectra have also been discussed.

A new bimetallic inorganic–organic hybrid {[Ru(phen)3](Pb3I8)}n (phen = 1,10-phenanthroline) (1) with its (Pb3I8)n2n− polymeric iodoplumbate templated by ruthenium complex [Ru(phen)3]2+, has been structurally determined. 1 is the rare example of mixed-metal iodoplumbate containing photochemically active coordination cation. The 1-D (Pb3I8)n2n− chain is constructed from edge-sharing of neighboring 2 × 3 Pb6I20 units. C–H···I hydrogen bonds among (Pb3I8)n2n− inorganic anions and [Ru(phen)3]2+ counteractions contribute to the formation of a 2-D layer. Moreover, its absorption spectrum and photoluminescence have also been discussed.

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.

A 3-D supramolecular hybrid {[La(EPC)3(H2O)3]2(Pb6I18)}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 (Pb6I18)n6n- zigzag-like anion chains with lanthanide metalcarboxylic [La(EPC)3(H2O)3]n3n+ 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 PbI2’s absorption edge.Highlights► Incorporating lanthanide metal-carboxylic coordination polycation into polymeric iodoplumbate to get heterometallic. ► (Pb6I18)n6n- anion chains and lanthanide metal-carboxylic [La(EPC)3(H2O)3]n3n+ polycations are in criss-cross configuration. ► semiconductor nature with optical gap of 2.46 eV.

Two new lanthanide–bismuth heterometallic hybrids, [Dy(DMF)8](Bi2I9) (1) and [Er(DMF)8](Bi2I9) (2) (N,N’-dimethylformamide (DMF)) have been synthesised by solution processes, which assume significance for their first incorporation lanthanide metals into bismuth iodides to get heterometallics. Two hybrids are isostructures containing (Bi2I9)3− halobismuthate dimers and lanthanide metal complexes [M(DMF)8]3+ (M = Dy, Er) cations, and it is noteworthy that the dimers and lanthanide metal complexes cations connect with each other by C–H···I hydrogen bonds to achieve the structural extending from 0-D to 1- or 2-D. Their absorption spectra and fluorescence’s were discussed, and energy band gaps of 2.19 eV indicate their narrow-gap semiconductor natures.

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.

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 hybrid iodoargentate [(APHEN-H)2(Ag4I6)]n (1) (APHEN = 5-amino-1,10-phenanthroline) has been obtained by the routine synthetic reaction and structurally determined. In 1, a (Ag4I6)n2- chain was defined by edge-sharing of Ag4I6 units, and its quasi-three-dimensional hybrid structure was constructed from π–π interactions and CH⋯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.

Two new neutral heterometallic iodoargentate hybrids, {[Cu(phen)2]2(Ag2I6)·(DMF)2}n (1) (phen = 1,10-phenanthroline) and {[Cu(bipy)(DMF)2](Ag7I9)}n (2) (bipy = 2,2′-bipyridine) have been obtained, in which copper–organic complexes covalently coordinate to iodoargentate skeletons. 1 exhibits a 3-D supramolecular framework based on hydrogen bonds and π⋯π stacking interactions among [Cu(phen)2]2(Ag2I6) clusters, and in 2, 2-D (Ag7I9)n2n− layers are linked by weak Cu–I bonds to give a 3-D framework. Their optical band gaps and magnetic properties have also been investigated.

Two iodoargentate hybrid solids {[Ni(2,2′-bipy)(THF)2(H2O)2](Ag10I12)·2DMF}n (1) and {[Cu(2,2′-bipy)3](Ag5I7)}n (2) (THF=tetrahydrofuran, DMF=N,N′-dimethyl formamide, 2,2′-bipy =2,2′-bipyridine) have been synthesized in a polar organic solvent, whose one-dimensional iodoargentate polymers are induced by second entrapped metal−organic complexes. In 1, the [Ag5I6]nn− chain exhibits a columnar structure based on an Ag5I6 quasi-pentagram building block. In 2, the zigzag chain [Ag5I7]n2n− is constructed from an Ag6I11 building block. Two compounds exhibit intriguing semiconducting properties with Eg = 2.74 and 2.80 eV. As indicated by density functional theory calculations, the observed strong photoluminescence in 1 arises from band-edge transitions.

Three hybrid polymeric iodoplumbates constructed from morpholine and its derivatives, {(Pb4I15)[(Mph·H)3(Mph·1.5H)2]}n(1), {(edm-H2)(Pb3I8)]·2DMF}n(2), {(edm-H2)[(dmp)(Pb4I12)]˙2DMF}n (3) (Mph = morpholine, edm = ethylenedimorpholine, dmp2+ = N,N′- dispiromorpholinopiperazonium) have been synthesized and structurally determined. In these compounds, morpholine and its derivatives weakly interact with or covalently bond to polymeric iodoplumbates. In 1, hydrogen bonds between (Pb4I15)7− clusters and protonized Mph contribute to the formation of a 1-D hybrid chain. In 2, the 1-D [(Pb3I8)]n2n− chain is extended to be a 2-D layer via the edm2+ ligand by means of Pb–O covalent bonds. Interestingly, the 2-D [(Pb4I12)]n4n− inorganic layer in 3 is concertedly templated by two kinds of organic cations. The above compounds exhibit a semiconductor nature, and third-order nonlinear optical (NLO) activities can be detected in 1 and 3.

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.

The hydrothermal reaction of Gd(NO3)3·6H2O with 2,2′-bipyridyl-4,4′-dicarboxylic acid(H2BPDC) ligand results in the formation of a new Gd(III) polymer: {[Gd2(BPDC)3(H2O)3]·H2O}n..(1). The central gadolinium ion is coordinated by eight oxygen atoms to give a dicapped triangular prism geometry. Based on the versatile coordination modes of BPDC2− ligand, together with hydrogen bonds and π···π stacking interactions, a 3-D network is presented. DFT calculation was executed to probe the electronic structure of 1.

Under the direction of large conjugated organic cationic SDAs (structure-directing agents), three silver(I) iodides, (ipq)4(Ag2I6·2I2) (1), {[pql][Ag2I3]}n (2), [(npql)2(Ag4I6)]n (3) (ipq+ = N-(isopentyl)-quinolinium, pql+ = N-propyl-quinolinium, npql+ = N-(n-pentyl)-quinolinium) have been synthesized. 1 presents a zero-dimensional structure constituting of ipq+ cations, [Ag2I6]4− anions and molecular iodine. But 2 and 3 consist of one-dimensional coordination polymers that could be described as edge-sharing AgI4 tetrahedra. Electrostatic interactions between organic counter cations and inorganic moieties are present and contribute to the crystal packing. The structural differences between 1, 2 and 3 illustrate the influences of substituents of SDAs on the linkage modes of AgI4 tetrahedra. DFT calculations were carried out to reveal their electronic structures.

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.

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 P1¯Z = 2, a = 10.4236(8) Å, b = 12.1950(9) Å, c = 15.6214(10) Å, 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) Å]. 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.

A 1-D hybrid copper(I) halides, [(phen)Cu3I3]n(phen = 1,10-phenanthroline)(1) with novel D6R (double six-membered rings) Cu6I6 cores, was synthesized by solvothermal reaction and characterized by single-crystal X-ray diffraction. In 1, nitrogen atoms from phen replace two I of CuI4 tetrahedron to give distorted tetrahedral geometries (CuI2N2), then CuI2N2 tetrahedron shares corners via μ3-I to generate an extended 1-D zigzag chain. Two zigzag chains combines with one 1-D (Cu4I4)n chain containing D6R cores via μ3-I-Cu (from cores) bonds to form the infinite 1-D ribbonlike polymer along the a-axis. Furthermore, the title compound is stabilized by conspicuous C–H···I hydrogen bonds, π–π and d10–d10 metallic interactions. Experimental and theoretical optical property investigation indicates that 1 possesses semiconductor property. DFT calculation was executed to probe the electronic structure of 1. To our interest, phen act as a property control species with its π* electrons appear in the forbidden band.

A new hybrid coordination polymer {[Cu(II)(2,2′-bipy)3][Pb2I6]}n (1) was synthesized by the reaction of Cu(NO3)2, 2,2′-bipy, PbI2 and NaI in DMF/DMSO mixed solvent. As revealed by X-ray structural analysis, 1 consists of [Pb2I6]n2n− polyanions and discrete [Cu(II)(2,2′-bipy)3]2+ structure-directing agent cations. The polymeric negative chain [Pb2I6]n2− is built up by face-sharing of PbI6 octahedra. Structure-directing reagent cations and polymeric negative chains are in combination with each other by static attracting force to form so-called hybrid structure. Experimental and theoretical optical property investigations indicate that 1 possesses semiconductor property. DFT calculation was executed to probe the electronic structure of 1. To our interest, when using both second metal and π system as electronic tuning species, conjugated system is more preferable.

A new type of hybrid semiconductor co-templated by both organic cations and inorganic polyiodide anions has been synthesized and structurally characterized. The Z-scan technique indicates that it also exhibits good third-order nonlinear optical activity.

Two new organically templated copper halides, (nbq)4Cu4I8 (1) and [(ipq)2(Cu5I7)]n (2) have been synthesized in the presence of nbq+ and ibq+ (nbq+ = N-(n-butyl)-quinolinium, ibq+ = N-(iso-pentyl)-quinolinium) acting as structure-directing agents(SDAs). Both of the compounds present hybrid structures with SDAs and inorganic moieties being incorporated. In 1, tetrameric Cu4I84− anion is composed by edge-sharing CuI4 tetrahedrons and CuI3 planar triangles. But the inorganic framework of 2 presents one-dimensional arrangement which results from the tetrahedron CuI4 and pseudo trigonal pyramid CuI3 through edge-sharing fashion. Electrostatic interactions between organic counter cations and inorganic moieties could be observed and contribute to the crystal packing. Both compounds are further characterized by IR, UV–Vis, elemental analysis, fluorescence and cyclic voltammetry.

Under the direction of large conjugated organic cationic SDAs (structure-directing agents), three silver(I) iodides, (ipq)4(Ag2I6·2I2) (1), {[pql][Ag2I3]}n (2), [(npql)2(Ag4I6)]n (3) (ipq+ = N-(isopentyl)-quinolinium, pql+ = N-propyl-quinolinium, npql+ = N-(n-pentyl)-quinolinium) have been synthesized. 1 presents a zero-dimensional structure constituting of ipq+ cations, [Ag2I6]4− anions and molecular iodine. But 2 and 3 consist of one-dimensional coordination polymers that could be described as edge-sharing AgI4 tetrahedra. Electrostatic interactions between organic counter cations and inorganic moieties are present and contribute to the crystal packing. The structural differences between 1, 2 and 3 illustrate the influences of substituents of SDAs on the linkage modes of AgI4 tetrahedra. DFT calculations were carried out to reveal their electronic structures.

Three hybrid polymeric iodoplumbates constructed from morpholine and its derivatives, {(Pb4I15)[(Mph·H)3(Mph·1.5H)2]}n(1), {(edm-H2)(Pb3I8)]·2DMF}n(2), {(edm-H2)[(dmp)(Pb4I12)]˙2DMF}n (3) (Mph = morpholine, edm = ethylenedimorpholine, dmp2+ = N,N′- dispiromorpholinopiperazonium) have been synthesized and structurally determined. In these compounds, morpholine and its derivatives weakly interact with or covalently bond to polymeric iodoplumbates. In 1, hydrogen bonds between (Pb4I15)7− clusters and protonized Mph contribute to the formation of a 1-D hybrid chain. In 2, the 1-D [(Pb3I8)]n2n− chain is extended to be a 2-D layer via the edm2+ ligand by means of Pb–O covalent bonds. Interestingly, the 2-D [(Pb4I12)]n4n− inorganic layer in 3 is concertedly templated by two kinds of organic cations. The above compounds exhibit a semiconductor nature, and third-order nonlinear optical (NLO) activities can be detected in 1 and 3.