•Three new extended supramolecular structures have been prepared.•They exhibit diverse structures and semiconducting properties.•The optical and electrical properties were also investigated.Construction of viologen cation salts of d10 metal halide anions (inorganic-organic hybrid materials) with semiconducting properties via supramolecular design and aggregate enable the hybrid materials multifunctionality. Our interest focused on the use of the viologen derivatives as the building units because they were redox-active units and more suited to yield new generation of multifunctional networks. In the present investigation, three new inorganic-organic hybrid semiconductors {[bbpyb]·[AgBr3]}n (1) [1, 3-PMBP][Zn2Cl5.1Br0.9] (2) and [1, 3-PMBP][Zn2Br6] (3) (bbpyb = 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium]bis[bromide], 1,3-PMBP = 1,1″-[1,3-phenylene-bis(methylene)]bis-4,4′-bipyridinium-bisbromide) were synthesized. More importantly, great efforts were devoted to investigate their properties, such as optical and electrical properties. 1–3 exhibited photochromism, which can be ascribed to the intermolecular charge transfer to yield radicals. Fabricating the appropriate inorganic and organic units controllably within photosensitive materials at a molecular level is critical for the development of new photochromic inorganic-organic hybrids.

Two novel complexes \(\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {(SCN)}_{4}]\}_{\mathrm{n}}\) (1) and \(\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {Br}_{4}]\}_{\mathrm{n}}\) (2) [Pepy=1-2-(Pyridinium-1-yl)-1-ethenyl) pyridinium] based on vinylpyridinium organic cation and cuprous salts have been synthesized and characterized by X-ray diffractometry. Compound 1 has a 2D polypseudorotaxane structure and compound 2 presents a 1D chain structure. Furthermore, the thermal gravimetric analysis (TGA), UV–Vis diffuse reflectance spectra, the morphology and the photocatalytic performances were studied carefully. Remarkably, both 1 and 2 exhibited good photocatalytic degradation abilities towards some dyes.

A series of organic–inorganic polypseudorotaxanes based on Cux(SCN)y polyanionic ring and bis(3,5-lutidine)alkyl dication threads are reported. This kind of interesting bis(pyridinium)alkyl template may facilitate the formation of 2D polypseudorotaxane. All these complexes exhibit excellent photochemical properties.

A new nanocrystalline inorganic–organic hybrid semiconductor [(BV)2(Ag5Br9)]n (1) with an intriguing windmill-like 1-D [Ag5Br9]nn− polymeric chain was assembled. Great efforts were devoted to investigate its semiconducting properties and applications, such as photoluminescence, emission decay lifetime, waste water purification, electrochemistry behavior and dielectric properties.

Three novel inorganic–organic supramolecular compounds based on cuprous halide/pseudohalides, named [MAPB][CuBr3] (1), [MAPB]2[Cu4I8] (2) and [(PAPB)Cu2(SCN)4]n (3), where MAPB = 1,3-bis(4-aminopyridiniummethyl)-benzene and PAPB = 1,4-bis(4-aminopyridiniummethyl)-benzene, have been synthesized based on a self-assembly reaction under ambient conditions. The structures of compounds 1, 2 and 3 were explored using IR spectroscopy, elemental analyses, PXRD, thermal gravimetric analysis (TGA), UV-Vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 is a mononuclear complex, compound 2 is a tetranuclear cubane-like clusteric oligomer and compound 3 possesses a 2-D polypseudorotaxane structure. Besides, the optical band gap and photocatalytic degradation properties of compounds 1–3 were also investigated and the excellent photodegradation efficiency of 2 may be due to the existence of distinct weak hydrogen bonds and face-to-face π–π stacking interactions.

•An interesting BiI3 oligomeric structure was prepared through solvothermal route.•Compound 1 is a 2D supramolecular network with channels.•It can readily and quickly adsorb rhodamine B (RhB) and methylene blue.The solvothermal reaction of a mixture of bismuth iodide, flexible cationic compound 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium] bis[tetrafluoroborate] (bbpyf) and HI at the temperature of 110 °C resulted in a novel compound, namely [bbpy][Bi4I16] (1). The structure of compound 1 was explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV–vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 was a 2D supramolecular structure consisted of one linear cationic compound bbpy2+ and inorganic anion cluster [Bi4I16]2− and contained a channel of 11.214 × 9.727 Å via noncovalent interactions. In addition, the adsorption behavior of 1 was also investigated. And it could adsorb methylene blue (MB) and Rhodamine B (RhB) from waste water fast and effectively, highlighting its potential application for environmental issues.

The hydrothermal reaction of a mixture of (NH4)6Mo7O24·4H2O, a flexible tripodal ligand 1,3,5-tris-(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and metal salts at different temperatures resulted in four novel compounds, namely [H2TITMB]2[Mo12O38]·4H2O (1), [Zn(Mo2O7)(TITMB)] (2), [H3TITMB]2[Cd(β-Mo8O26)(H2O)2(α-Mo8O26)]·4H2O (3) and [H3TITMB]2[Co(β-Mo8O26)(H2O)2(α-Mo8O26)]·4.5H2O (4). The structures of compounds 1, 2, 3 and 4 were explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV-vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. In 1 the new type of isopolymolybdate unit [Mo12O38]4− shared ten distorted {MoO6} octahedra and two distorted {MoO5} tetragonal pyramid with four kinds of O atoms. And the unprecedented bimetallic oxide chain [Zn(Mo2O7)]n in compound 2 consisted of trigonal bipyramids and octahedra through sharing edges. Both compounds 3 and 4 are 3-D octamolybdate-based inorganic–organic hybrids consisting of the polyacid [α-Mo8O26]4− anions and novel infinite chains of [β-Mo8O26]4− anions covalently linked through [Cd(H2O)2]2+ groups or [Co(H2O)2]2+ groups. In addition, the electrochemical behavior and photocatalytic activities of the title compounds were also investigated.

Two novel complexes based on multivalent organic cations and PbI2, {(tbp)2[Pb3I12]}n (1) (tbp = 1,3,5-tri(N-pyridinium methyl)benzene tribromide) and {(tbpm)[Pb3I9]·H2O}n (2) (tbpm = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide), have been synthesized and characterized by X-ray diffractometry. Compound 1 has a trinuclear structure and compound 2 presents a new 1D iodoplumbate. Photochemical studies reveal the good photocatalytic performances of the two iodoplumbate hybrids. Furthermore, the side chain's effect on the fabrication of the iodoplumbate and the photocatalytic performances was also investigated.

•Five novel haloclusters were synthesized by the cation-templated self-assembly.•These compounds were all composed of discrete cations and haloclusters anions.•Complex 1 is a rare 2D polypseudorotaxane structure.•The anion portion exhibit different configurations by varying the alkyl chain length.Under the direction of dicationic bolaamphiphiles as SDAs (structure-directing agents), five new cuprous/silver halides(pseudohalides) formulated as {[BMIE][Ag2Br4]}n (1), {[BMIE][Ag2I4]}n (2), {[BMIB][Ag2Br4]}n (3), {(BDMIH)[Cu4(SCN)6]}n (4) and {[BDMIO][Cu2(SCN)4]}n (5) [BMIE·2Br = 1,2-bis(3-methylimidozole-1-yl) ethane dibromide, BMIB·2Br = 1,4-bis(3-methylimidozole-1-yl) butane dibromide, BDMIH·2Br = 1,6-bis(2,3-dimethylimidozole-1-yl)hexane dibromide, BDMIO·2Br = 1,8-bis(2,3-dimethylimidozole-1-yl)octane dibromide] were synthesized by self-assembly strategy in DMF–MeOH system. The X-ray crystallography analysis showed that these compounds were all composed of discrete organic cations and halocluster anions interacted by electrostatic interactions and hydrogen bonds. Compound 1 exhibits two-dimensional polypseudorotaxane structure. Compounds 2–4 present one-dimensional chain structure, compound 5 has a one-dimensional ladder-like structure. These compounds were characterized by IR, UV–Vis, PXRD and TGA. Their luminescent properties were further investigated in the solid state.Graphical abstractFive novel haloclusters possess 0–2D frameworks were prepared by the directing of cationic bolaamphiphiles template. The anion portion exhibit different configurations by varying the alkyl chain length.

•Five new haloclusters were synthesized by the cation-templated self-assembly.•These compounds were all composed of discrete cations and haloclusters anions.•Trivalent cation adopted interesting cis–cis–cis or cis–trans–trans configurations.•In 2 the direction of same template generates two kinds of coexisting halocluster anions.•Complex 5 is a rare 2D polypseudorotaxane structure.Five new haloclusters, namely, {[Tbmpm](MeOH)[Cu3Br6]} (1), {[Tbmpm][Cu2(SCN)5]}n (2), {[Tbmpm][Ag4Br7] }n (3), {[Tbmpm]0.5[Ag2Br2.2(SCN)0.7]}n (4) and {[Tbpm][Cu2(SCN)5]}n (5) [Tbmpm·3Br = 1,3,5-tri(4-methylpyridiniummethyl)-2,4,6-trimethylbenzene tribromide and Tbpm·3Br = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide] were synthesized by the cation-templated self-assembly with Cu/AgX (X = Br, I, SCN) in N, N-dimethyl formamide (DMF) and MeOH system. The X-ray crystallography analysis showed that these compounds were all composed of discrete organic cations and halocluster anions. Compound 1 has a trinuclear structure, compound 2 exhibits an anion complex composed of 1D chain and mononuclear structure, compounds 3 and 4 present similar 1D silver cluster. More interesting, compound 5 possesses a rare 2D polypseudorotaxane structure. The H-bonds and electrostatic interactions between the organic counteractions and inorganic moieties also do the contribution to the crystal packing. These compounds were further characterized by IR spectra, UV–Vis, PXRD, and thermal gravimetric analysis (TGA). Their luminescent properties were also investigated in the solid state.Cation-templated self-assembly generated five new haloclusters comprising of 0-2D supramolecular anion frameworks. Organic cation adopted less common cis–trans–trans mode in complexes 2 and 5. There are two kinds of coexisting halocluster anions in compound 2. Complex 5 is a rare 2D polypseudorotaxane structure.

•Two Ag (I) photoresponsive metal–organic complexes were synthesized.•Compound 1 included a crown-like anion construction.•Compounds 1 and 2 may be a kind of fast photo-response material.Two Ag (I) photoresponsive metal–organic complexes have been constructed from viologen derivatives 1, 1″-[1, n-phenylene-bis(methylene)]bis-4, 4′-bipyridinium-bisbromide (n = 2 and 3) cationic ligands and silver bromide upon slow self-assembly at room temperature. They are characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermal gravimetric analysis (TGA), UV–vis, IR and ESR spectra. Compound 1 is a 3D folding framework and compound 2 contains a 1D inorganic chain constructed by (AgBr3)2 − polyhedral units. In addition, the photochromic behaviors of compounds 1 and 2 were also investigated, and they show different and obvious fast photoresponse rate under sunlight.Two Ag (I) photoresponsive metal–organic complexes with different and obvious fast photoresponse rate under sunlight have been constructed from viologen derivatives 1, 1″-[1, n-phenylene-bis(methylene)]bis-4, 4′-bipyridinium-bisbromide (n = 2 and 3) cationic ligands and silver bromide upon slow self-assembly at the room temperature.

•The side chain effect in stoppers facilitates the fabrication of polypseudorotaxane.•The photocatalytic performances of these compounds are well.•Complexes 2, 3 and 5 show strong photoluminescence.Cation-templated self-assembly of 1,n-bis(4-methylpyridine)alkane cations (n = 3–7) with CuSCN was studied and a series of new polymeric thiocyanate frameworks were obtained: {(bmpp)[Cu2Br2(SCN)2]}n (1), {(bmpt)[Cu2(SCN)4]}n (2), {(bmppt)[Cu2(SCN)4]}n (3), {(bmph)[Cu4(SCN)6]}n (4), {(bmphp)[Cu2(SCN)4]}n (5), (n = 3, bmpp; n = 4, bmpt; n = 5, bmppt; n = 6, bmph; n = 7, bmphp). The structures consist of 1-2D frameworks with the dications trapped within host network cavities. Compounds 1, 2, 3 and 5 possess the infinite two-dimensional polypseudorotaxane anion networks. Compound 4 has a novel 1D chain structure which looks like lotus root. The results demonstrate that the side chain of methyl substituent plays an important role in the fabrication of polypseudorotaxane structures. Furthermore, solid UV–Vis spectra, photoluminescence and photocatalytic properties at ambient temperature were also investigated.We report five novel extended supramolecular polymers based on CuSCN and 1,n-bis(4-methylpyridine)alkane cations. Compounds 1, 2, 3 and 5 possess the infinite two-dimensional polypseudorotaxane anion networks. Compound 4 has a novel 1D chain structure which looks like lotus root.

•Compound 1 exhibits a 3D polypseudorotaxane network.•Compounds 2, 3 display 2D sandwich architecture.•Compounds 4 and 5 present 2D polypseudorotaxane layer.•SCN− can present all five coordinating modes.The N-1-methylimidazole-substituted multication-templated self-assembly of CuSCN/AgSCN leads to five novel complex salts: {(tbi)[Cu3(SCN)6]}n (1), {(tbmi)[Cu2(SCN)5]}n (2), {(tebi)[Cu(SCN)2]4}n (3), {(tebi)[Cu(SCN)2]4}n (4) and {(tbmi)2[Ag5(SCN)11]}n (5) [tbi3+ = 1,3,5-tri[3′(1′-methyl)imidazoliummethyl]benzene, tbmi3+ = 1,3,5-tri[3′-(1′-methyl)imidazoliummethyl]-2,4,6-trimethylbenzene and tebi4+ = 1,2,4,5-tetra[3′-(1′-methyl)imidazoliummethyl]benzene]. Single-crystal X-ray diffraction shows that 2, 3 and 5 display a 2D sandwich structure, 4 presents a 2D polypseudorotaxane network, whereas, 1 exhibits a 3D polypseudorotaxane architecture. It is worth noting that SCN− can present five coordinating modes. All these results confirm the versatile template effect and correct choice of multications. In addition, elemental analysis, IR and UV–Vis spectra, powder X-ray diffraction patterns, thermogravimetric analyses of these complexes have been investigated.Inspired by the lack of supramolecular hybrids induced by the multivalent interactions, we conducted five integrations of trication or tetracation with thiocyanates via strict templated self-assembly. These compounds 1, 4, and 5 represent the first type of 2–3D polypseudorotaxane nets.

Three novel cation-templated complexes, {(dmb)[Pb2Cl2I4]}n (1), {(ddb)[Pb2I6]}n (2), {(dmh)[Pb2I6]}n (3) (dmb = α,α-di(3-methylimidozole-1-yl)benzene dichloride, ddb = α,α-di(2,3-dimethylimidozole-1-yl)benzene dichloride, dmh = 1,6-di(3-methylimidozole) hexane have been synthesized via the self-assembly reaction in solution. The X-ray crystallography shows these compounds were all composed of imidazole organic dications and halocluster anions. It is the H-bonds and electrostatic interactions between the organic counteractions and inorganic moieties that do the contribution to the crystal packing. These compounds have been further characterized by IR spectroscopy, UV–Vis spectra and thermostability properties.

Two novel cation-templated complexes, {(1, 4-PMBP)[Pb4I10] ⋅DMF}n(1) {(DBBP)2[Pb5I8Br6]}n(2), (1,4-PMBP ⋅2Br =1,1”-[1,4-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide; DBBP ⋅2Br = N, N’-dibenzyl- 4, 4’-bipyridinium dibromide) have been synthesized via the self-assembly reaction in solution. X-ray crystallography showed that compounds 1 and 2 can be regarded as 1D iodoplumbate examples which contain incomplete cubane subunit directed by π-conjugated dication templates. It is the H-bonds and electrostatic interactions between the organic counter cations and inorganic moieties that contribute the crystal packing. These compounds have been further characterized by IR spectroscopy, UV-Vis spectra, elemental analysis and thermostability properties.

Highlights•Cation-templated self-assembly of eleven polyoxometalates has been performed.•Most anions possess β-octamolybdate isomeric structure.•These geminal dications can serve as efficient candidate for β-isomer recognition.Eleven novel polyoxometalates, namely [1,1′-(alkane-1,ω-diyl)-bis(3-methylimidazolium)]m [Mo8O26][nH3O+]·xH2O (ω = 1–11; m = 1, 1.5, 2; n = 0, 1; x = 0, 1, 2) were synthesized by the self-assembly with octamolybdate anions under hydrothermal reaction conditions. The crystal data analysis revealed that these compounds were all composed of discrete methylimidazolium cations and polyacid anions [Mo8O26]4− interacted by electrostatic interactions and hydrogen bonds. Interestingly, the anions of these compounds took on single [β-Mo8O26]4− cluster, twin [β-Mo8O26]4− clusters, a δ-[Mo8O26]4− cluster and a rare 1D 1/∞[β-Mo8O26]4− polymeric chain with the modification of lengths of alkane components.Cation-templated self-assembly of eleven polyoxometalates has been performed, and most anions possess β-octamolybdate isomeric structure, which shows that these geminal dicationic ionic liquids can serve as an efficient candidate for β-isomer recognition.

Highlights•Through dication templated self-assembly six novel haloclusters were synthesized.•Compounds 2, 4 and 6 consisted of composite chains with metal–metal interaction.•While compounds 1, 3 and 5 comprise 0–1 dimensional anion framework.•The subtle template effect between dbm and ddb were compared.Six novel haloclusters, namely {[dmb]2[Cu4I8]}·2DMF (1), {[ddb][Cu4I6]}n (2), {[dmb][Ag2I4]}n (3), {[ddb][Ag4I6]}n (4), {[dmb]2[Ag2Br6]} (5) and {[ddb][Ag4Br6]}n (6), were encountered in our investigation of the subtle template effect of methyl substituent on the formation of hybrids. The dications we chosen as C2-symmetric template is α,α′-di(3-methylimidozole-1-yl)benzene dichloride (abbreviated into dmb) or α,α′-di(2,3-dimethylimidozole-1-yl)benzene dichloride (abbreviated into ddb). The X-ray crystallography shows the more methyl substituents that exist in template, the more inorganic/organic interactions form in the hybrid net oriented by ddb. It is the H-bonds and electrostatic interactions between the organic counteractions and inorganic moieties that do the contribution to the crystal packing. These compounds have been further characterized by IR spectroscopy, UV–Vis spectra and thermostability properties.Six novel dication-directed haloclusters comprising of 0–1D supramolecular anion frameworks together with the subtle template effect of methyl group were reported.

The reaction of CuSCN (or CuCl2) in the presence of excess KSCN directed by viologen-based linear templates in a dimethyl formamide–methanol system affords six coordination polymers, {(MV)[Cu2(SCN)4]}n (1, MV2+ = 1,1′-dimethyl-4,4′-bipyridinium), {(PrV)[Cu2(SCN)4]}n (2, PrV2+ = 1,1′-dipropyl-4,4′-bipyridinium), {(iPV)[Cu2(SCN)4]}n (3, iPV2+ = 1,1′-diisopropyl-4,4′-bipyridinium), [(1-iBV)Cu2(SCN)3]n (4, 1-iBV2+ = 1-isobutyl-4,4′-bipyridinium), {(iBV)[Cu2(SCN)4]}n (5, iBV2+ = 1,1′-diisobutyl-4,4′-bipyridinium), and {(PtV)[Cu2(SCN)4]}n (6, PtV2+ = 1,1′-dipentyl-4,4′-bipyridinium). The [Cu2(SCN)4]n anion in compounds 1, 3 and 5 adopts an infinite two-dimensional polypseudorotaxane architecture and proved effectively that the stoppers at the end can enhance the polyrotaxane formation in the crystalline state, whereas the anion moieties in compounds 2 and 6 exhibit one-dimensional linear architectures, suggesting dethreading from envelopes once solidifying from solution phase. Compound 4 was found to be a two-dimensional coordination polymer with the organic ligand carrying a single charge. The side chain template effect of substituted group, UV-Vis diffuse reflectance spectra in the solid state and TGA properties of the six complexes are investigated.

Inspired by the lack of supramolecular hybrids induced by the multivalent interactions, we conducted three integrations of trication or tetracation with thiocyanate via strict templated self-assembly. These compounds represent the first type of 2–3 dimensional multi-threading polypseudorotaxanes based on Cu6(SCN)6 macrocycles.

Trication-templated assembly of POMs resulted in an unprecedented ι-type octamolybdate configuration. The ι-[Mo8O26]4− cluster is composed of five {MoO6} octahedra and three {MoO4} tetrahedra via an edge-sharing and corner-sharing arrangement to form a cabas-like cluster, which represents the ninth isomer of octamolybdates.

Six novel molybdenum hybrid materials based on a flexible multidentate ligand, namely (H3tib)4(β-Mo8O26)3·5H2O (1), (H3tib)2[Cu(H2O)2(γ-Mo8O26)2]·2H2O (2), [Cu(Htib)2(δ-Mo8O26)]·4H2O (3), [Cu2(tib)2(H2O)2(γ-Mo8O26)]·H2O (4), (H3tib)2[Co(H2O)2(γ-Mo8O26)2]·2H2O (5), and Zn(tib)(MoO4)·3H2O (6) (where tib = 1,3,5-tris(imidazol-1-ylmethyl)benzene), have been synthesized at different pH values under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analysis and further characterized by PXRD, TGA, IR spectra, and electrochemistry. Compound 1 is a supramolecule with classical β-Mo8O26 cages. Compounds 2 and 5 exhibit a rare one-dimensional (1D) molybdenum oxide duplex chain. We have not yet found any other examples of the two adjacent 1D molybdenum oxide chains linked together through the centers of the Cu/Co cations. In 3, the CuII cations are bridged by Htib+ ligands and (δ-Mo8O26)4− anions to form an interesting two-dimensional (2D) layer. In 4, the CuIIcations, tib ligands and (γ-Mo8O26)4− anions are connected to form a 2D layer, which is further reinforced by the tib ligands through an Mo–N bond. Compound 6 is a 2D coordination polymer possessing a high thermal stability. The structural diversities of 2–4 reveal that the pH value of the reaction system, the metal coordination preference and the ligand configuration play a crucial role in the assembly of POM-based complexes.

Ten novel cation-induced complexes, {(BIQPT)2[Ag2I6]} (1), {[(BIQBT)CuI3]} (2), {(BIQHX)2[Cu4I8]·DMF} (3), {(BIQBT)1.5[MoOS3Cu3I4]·DMF} (4), {(BIQHX)[Ag4Br6]}n (5), {[(BIQHX)Ag4I6]}n (6), {(BIQHX)[Cu2(SCN)4]}n (7), {(BIQBT)[Cu2(SCN)4]}n (8), {(BIQPP)[Cu2(SCN)4]}n (9), {(BIQEH)[Cu2(SCN)4]}n (10) {BIQPT = 1,5-bis(isoquinoline)pentane, BIQBT = 1,4-bis(isoquinoline)butane, BIQHX = 1,6-bis(isoquinoline)hexane, BIQPP = 1,3-bis(isoquinoline)propane, BIQEH = 1,2-bis(isoquinoline)ethane} have been constructed via anion exchange reaction of bis(isoquinoline) ionic liquids. In these ten compounds, the anion structures ranged from mononuclear (2), dimer (1), tetranuclear oligomer (3 and 4), to 1D chain (5, 6,7 and 8) and 2D polymeric architectures (9 and 10). These results indicated that anion exchange reaction is an efficient approach for the preparation of cluster-functionalized ILs or IL-functionalized MOFs.

Four novel heterothiometallic cluster polymers based on a [MoOS3Cu3] unit have been synthesized by the solution self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MoS2O2 and CuX (X = I, Br, or SCN) in the presence of different organic cation-templates [DMI]·I, [C6(Mim)2]·Br2, [C3(Mim)2]·Br2, and [BBP]·Br2: Compounds {[MoOS3Cu3I(μ-bpy)2.5]·2.5DMF}∞ (1), {[MoOS3Cu3I(μ-bpy)2.5] ·DMF}∞ (2), and {[MoOS3Cu3Br(μ-bpy)2.5]·2.5DMF}∞ (3) are isomorphous neutral 3D 4-fold interpenetrating architectures with a (6, 4) node, while polymer [MoOS3Cu3(NCS)(μ-bpy)2.5]∞ (4) is a 3D architecture with a (64 82) net displaying self-interpenetrating features. All of them have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and UV-vis. The results may provide fascinating insights into the template effect on the construction of the cluster-based coordination polymers.

12 new cation-templated complexes, {(BMPB)[AgI3]} (BMPB = 1, 4-bis (methylpyridinium) benzene) (1), {(BPE)2[Ag2I6]} (BPE = 1, 2-bis (pyridinium) ethane) (2), {(BPB)[Ag2I4]} (BPB = 1, 4-bis (pyridinium) butane) (3), {(BPH)[Ag2I4]} (BPH = 1, 7-bis (pyridinium) heptane) (4), {(DIBP)[Ag2I4]} (DIBP = 1, 1′-diisopropyl-4, 4′-bipyridinium) (5), {(BPB)[Ag2Br4]} (6), {(BPP)[Ag2Br4]} (=1, 5-bis (pyridinium) pentane) (7), {(DEBP)[Ag2Br4]} (DEBP = 1, 1′-diethyl-4, 4′-bipyridinium) (8), {(BDMLB)[Ag2Br4]} (BDMLB = 1, 4-bis (dimethylimidazolium) butane) (9), {(BPIB·Br)[Ag(NCS)2]} (BPIB·Br = butane phenanthroline bromide) (10), {(DABP)[Ag4I6]} (DABP = 1, 1′-diamyl-4, 4′-bipyridinium) (11), {(BMLB)[Ag2Br2(NCS)2]} (BMLB = 1, 4-bis (methylimidazolium) butane) (12), have been synthesized via the self-assembly reaction in solution. Owing to the cooperative template effects from organic cations and halide/thiocyanate anion compounds 1–11 contain a mononuclear anion structure [AgI3]2− (1), a dimeric anion [Ag2I6]4− (2), linear chain [Ag2X4]2− (3–10) and a cubane-like based one-dimensional anionic chain [Ag4I6]2− (11) that are enclosed into the different cationic channels formed from the pyridinium, phenanthrolinium and imidazolium. While for 12, the compound possesses an infinite 2D supramolecular polypseudorotaxane penetrated by geminal dicationic groups.

Three novel cation-templated complexes, {(BPE)3[Ag4Br4(SCN)6]}n (1), {(DEBP) [Cu2(SCN)4]}n (2) and {(DIBP) [Cu2(SCN)4]}n (3) [BPE = 1, 2-bis (pyridinium) ethane; DEBP = 1, 1′-diethyl-4, 4′-bipyridinium dibromide; DIBP = 1, 1′-diisopentyl-4, 4′-bipyridinium], have been synthesized viaself-assembly reaction in solution. Complex 1 possesses a one-dimensional polyrotaxane architecture with the organic cation BPE trapped in it, whereas both compounds 2 and 3 are infinite 2D supramolecular polypseudorotaxane, linked by bridging thiocyanate groups. All compounds were further characterized with IR spectra, thermal analysis, ultraviolet and fluorescence properties.

In our effort to systematically investigate the influence of spacers and terminal groups in structure-directing agent BBP on Ag/I, Pb/I and Cu/SCN inorganic frameworks, four coordination polymers, {[(Ag2I6)(BBP)2]} (1), {[(Pb6I22)(DMF)2(BBP)5]} (2), {[Cu2(SCN)4(BBP)]}n (3) and {[Cu4(SCN)6(BBP)]}n (4) have been synthesized in polar organic solvents. Compound 1 is a dimer of [Ag2I6]2−; compound 2 is a hexanuclear oligomer of [Pb6I22]10−; both compound 3 and 4 are infinite Cu(I) supramolecular polymers linked by bridging thiocyanate groups; whereas compound 3 possesses a 1D chain structure, compound 4 exhibits a two-dimensional cubane-based polypseudorotaxane network. All compounds were further characterized with elemental analysis, IR spectra, thermal analysis, and fluorescence properties.

Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = Cl, NCS) in the present of 1,1-bis(pyridinium)methylene [bpm = 1,1′-bis(pyridinium)methylene] resulted in four novel neutral heterothiometallic cluster polymers based on tetranuclear [Mo/WOS3Cu3] unit: [MOS3Cu3Cl(μ-bpy)2·Sol]n (M = Mo, Sol = 1.3DMF·5.5H2O 1; M = W, Sol = 1.5DMF·8.2H2O 2), [MoOS3Cu3(NCS)(bpy)(μ-bpy)2·DMF]n (3), and [WOS3Cu3(NCS)(μ-bpy)2.5·3DMF]n (4). Polymer 1 or 2 crystallizes in the Fddd space group with a 2-fold interpenetrating (10,3)-b net, which presents a 3-connected 3D heterothiometallic polymer assembled with bidentate organic bridging ligands. Polymer 3 crystallizes in the space group P1 with a 2D noninterpenetrating network with (6,3) topology in which [MoOS3Cu3(bpy)] units are interconnected via three single or double Cu-μ-bpy-Cu bridges. Polymer 4 crystallizes in the space group C2/c with a (64 82) net, which displays the first self-interpenetrating network in heterothiometallic chemistry. All of these results confirm the ideal template effect and correct choice of bpm.

Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = 4,4′-bipyridine) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = I) in the presence of bppt [bppt = 1, 5-bis (pyridinium) pentane] resulted in two novel neutral heterothiometallic cluster polymers: {[Mo2O2S6Cu6BrI(4,4′-bipy)4] (4,4′-bipy)}n (1) and {[WOS3Cu3Br(4,4-bipy)2.5]·3 (DMF)}n (2). Compound 1 exhibits a neutral 3D 3-fold interpenetrating motif and compound 2 possesses a neutral 3D 4-fold interpenetrating architecture. Both of them have been characterized by IR, elemental analysis, TGA, UV–vis, PXRD, and single-crystal X-ray diffraction. The results may provide fascinating insights into the usage of template effect on the construction of the cluster-based coordination polymers.Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = I) in the presence of bppt (bppt = 1, 5-bis (pyridinium) pentane) resulted in two novel neutral heterothiometallic cluster polymers: {[Mo2O2S6Cu6BrI(4,4′-bipy)4]. (4,4′-bipy)}n (1) and {[WOS3Cu3Br(4,4-bipy)2.5].3 (DMF)}n (2). Compound 1 is a neutral 3D 3-fold interpenetrating network and compound 2 is a neutral 3D 4-fold interpenetrating architecture. Both of them have been characterized by single-crystal X-ray diffraction, elemental analysis, PXRD, IR, TGA, and UV–vis. The results may provide fascinating insights into template effect on the construction of the cluster-based coordination polymers.Highlights► The first assembly of heterothiometallate with 1, ω-bolaamphiphile cation-template.► Compound 1 is a neutral 3-fold interpenetrating network. ► Compound 2 is a neutral 4-fold interpenetrating diamondoid network. ► The temporary cation template played a crucial role in building the polymers.

A novel coordinated polymer [HgI2(4-bped)2] was synthesized through the reaction of bis(4-pyridyl)ethylene diamine and HgI2 in mixed MeOH–THF (5:2). The crystal structural analysis indicated that the complex crystallized in a monoclinic space group P21/c, a = 10.8392(12), b = 19.841(2), c = 8.8279(10), β = 95.452(2), V = 1889.9(4) Å3, Z = 4. The complex possessed a novel three-dimensional supramolecular framework formed by hydrogen bonds among repeating [HgI2(4-bped)]2 dimeric units.

In this article, solution reaction of cadmium iodide with organic multifunctional ligand 1,1′-(1,4-butanediyl)bis-1H-benzotriazole(bbbt) generated a 1D polymer [CdI2 (bbbt) (CH3OH)]n1, and the crystal structure has been determined (C17 H20 Cd I2 N6 O), Mr = 690.59 a = 10.032(2), b = 13.503(3), c = 16.706(3) Å, space group C2/c,Z = 4, and V = 2223.1(8) Å3. In 1 the tetrahedral coordination of Cd(II) and the conformation of bbbt ligand make it a wave-shaped structure.

A new coordination polymer based on Group IB metal thiocyanates, [Ag2I (NCS)2(dpds)2]n (1) (dpds = 2,2′-dipyridyldisulfide), has been synthesized by the pre-assembly method and characterized by X-ray crystallography. In 1, the AgI center adopts tetrahedral coordination geometry and the 2-D undulated layers of (4, 4) topology network is formed by dpds ligand with zigzag NCS−Ag chains.

Self-assembly of a series of effective cation-templates with [Mo(W)/Cu/S]-based clusters was studied. Permanent templated products {(bppp)[MoOS3Cu3I3(4,4′-bipy)1.5]}n (1), {(bpbt)[MoOS3Cu3I3(4,4′-bipy)1.5]}n (2), {(bppp)[WOS3Cu3I3(4,4′-bipy)1.5]}n (3), and {(bpbt)[WOS3Cu3Br3(4,4′-bipy)1.5]}n (4) show 1D anionic zigzag pattern (bppp = 1,3-bis(pyridinium) propane, bpbt = 1,4-bis(pyridinium) butane). Compounds 1–4 have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, UV–vis and thermogravimetric Analysis. The results may provide fascinating insights into template effects on the construction of the cluster-based coordination polymers and that coordination modes of compounds 3 and 4 have not been found in the reported one-dimensional zigzag coordination polymers.

Two novel cation-induced complexes, {(Phen-dq) [Cu2(SCN)4]}n (1) and {(Phen-dzp) [Cu2(SCN)4]}n (2) [Phen-dq = (C14H12N2)2+, 5,6-dihydropyrazino[1, 2, 3, 4-lmn]-1, 10-phenanthrolinium, Phen-dzp = (C15H14N2)2+, 6,7-dihydro-5H-[1, 4]diazepino[1, 2, 3, 4-lmn][1,10]phenanthroline-4, 8-diium], have been synthesized via the self-assembly reaction in solution. The compound 1 possesses a two-dimensional supramolecular network linked by bridging thiocyanate groups. Complex 2 is also a two-dimensional polymeric architecture with the organic cation Phen-dzp trapped in it. Each Cu(I) atom is coordinated by two N atoms and two S atoms from four NCS groups to form a Cu2(NCS)2 rectangular dimer unit. In these two compounds, thanks to the difference from organic cations, the simple modification from Phen-dq to Phen-dzp leads to distinct structures between 1 and 2, and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.Two novel cation-induced complexes, {(Phen-dq) [Cu2(SCN)4)]}n (1) and {(Phen-dzp) [Cu2(SCN)4]}n (2) [Phen-dq = (C14H12N2)2+, 5,6-dihydropyrazino[1, 2, 3, 4-lmn]-1,10-phenanthrolinium, Phen-dzp = C15H14N2)2+, 6, 7-dihydro-5H-[1, 4]diazepin-o[1, 2, 3, 4-lmn] [1, 10] phenanthr-o-line-4, 8-diium], have been synthesized. In these compounds, the simple modification from Phen-dq to Phen-dzp leads to distinct structures between 1 and 2, and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.

In this paper, solution reaction of cadmium iodide with organic multifunctional ligand 1,4-bis(benzimidazole-1-yl-methylene)benzene generated a 1D polymer [CdI2 (bbmb). (DMF) (CH3CN)]n1, and the crystal structure has been determined (C27H28CdI2N6O), Mr = 818.75, a  = 14.929(1) Å, b = 17.381(2) Å, c = 15.850(1) Å, β = 114.8190(10)°, space group C2/c, Z = 4, and V = 3733.3(6) Å3. In 1 the tetrahedral coordination of Cd(II) and the conformation of the bbmb ligand make it a wave-shaped structure.Synthesis and structure of a CdI2 coordination polymer with 1,4-bis(benzimidazole-1-yl-methylene)benzene(bbmb)Xiucun Liu, Xiaoling Guo, Yunyin Niu, Qingli Wang, Qian Cui, Hongwei Hou, Xiaorui Lv, SeikWeng Ng

The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. Single crystal X-ray diffraction analysis established that the compound crystallizes in the monoclinic system, space group C2/m, with a = 15.601(3), b = 12.438(3), c = 12.570(3)Å, β = 110.02(3), Z = 4, V = 2291.8(8)Å3. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu2I2 cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state.The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu2I2 cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state.Open image in new window

The solution-phase reaction of HgCl2 with benzyldiphenylphosphine (PPh2Bz) yields a new triaryl phosphine complex [HgCl2(PPh2Bz)2] (1) with the bigger P–Hg–P angle, the longer Hg–Cl bond, and the shorter Hg–P bond. Comparison of the sensitive bond parameters with similar compounds and the theoretical calculation show that the σ-donating abilities of tertiaryl phosphine ligands toward HgCl2 conforms to the following order: PEt3 > PPh2Bz > P(2-thienyl)3 > dppf > PPh3.The solution-phase reaction of HgCl2 with benzyldiphenylphosphine (PPh2Bz) yields a new triaryl phosphine complex [HgCl2(PPh2Bz)2] (1) with the bigger P–Hg–P angle. Comparison of the sensitive bond parameters with similar compounds shows that the σ-donating abilities of tertiaryl phosphine ligands toward HgCl2 conforms to the following order: PEt3 > PPh2Bz > P(2-thienyl)3 > dppf > PPh3. Open image in new window

Cation-templated self-assembly of 1,ω-bis(pyridinium)alkanes (ω = 1−6) with cuprous thiocyanate was studied, and six sparse polymeric thiocyanate frameworks were obtained and characterized by X-ray crystallography: {(bpm)[Cu(NCS)4]}n (1), {(bpe)[Cu2(NCS)4]}n (2), {(bppp)[Cu(NCS)3]}n (3), {(bpbt)[Cu(NCS)4]}n (4), {(bppt)[Cu2(NCS)4]}n (5), and {(bph) [Cu2(NCS)4]}n (6) (bpm = 1,1′-bis(pyridinium)methylene, bpe = 1,2-bis(pyridinium)ethane, bppp = 1,3-bis(pyridinium)propane, bpbt = 1,4-bis(pyridinium)butane, bppt = 1,5-bis(pyridinium)pentane, bph = 1,6-bis(pyridinium) hexane). The structures consist of 0−3-dimensional frameworks with the bispyridinium cations trapped within host network cavities. Compound 1 has a 3D porous (6,3)/(6,4) joint topology structure, compounds 2 and 5 have two-dimensional polypseudorotaxane interlocked structures, compound 3 has a dimeric structure, compound 4 has a two-dimensional honeycomb structure, and compound 6 exhibits an interesting 1D hanging ladder-shaped complementary chain structure. The third-order NLO effect of 3 was studied by Z-scan techniques. The dimer exhibits self-focusing optical nonlinearities, and the effective third-order NLO refractive index (n2) value is 3.03 × 10−11 esu.

Reaction of the ligand N,N′-(1,2-phenylene)diisonicotinamide (pia) with metal(II) salts MSO4 [M = Cu(II), Zn(II)] leads to the formation of two 2D coordination networks [(CuSO4)(pia) · 2CH3OH · H2O]n (1) and [(ZnSO4)(pia) · 2H2O]n (2). In the solid state of 1 the Cu(II) center adopt a five-coordination square pyramidal geometry, and the network is generated through the interconnection of the pia organic moieties by [Cu2(SO4)2] dimers resulting in a 2D motif containing irregular inner cavities for guest molecule inclusion; in the case of 2, the Zn(II) center adopt a tetrahedral coordination geometry and the 2D network is formed by pia with another type of connector, zigzag SO42-–Zn chains. Compound 2 displays intense photoluminescence in the solid state at room temperature upon photo-excitation at 245 nm. The photoluminescence behaviors of the polymer 2 are related to the intraligand emission excited state.Reaction of the ligand N,N′-(1,2-phenylene)diisonicotinamide (pia) with metal(II) salts MSO4 [M = Cu(II), Zn(II)] leads to the formation of two 2D coordination networks [(CuSO4)(pia) · 2CH3OH · H2O]n (1) and [(ZnSO4)(pia) · 2H2O]n (2). In the solid state of 1 the Cu(II) center adopts a five-coordination square pyramidal geometry, and the network is generated through the interconnection of the pia organic moieties by [Cu2(SO4)2] dimers resulting in a 2D motif containing irregular inner cavities for guest molecule inclusion; in the case of 2, the Zn(II) center adopts a tetrahedral coordination geometry and the 2D network is formed by pia with another type of connector, zigzag SO42-–Zn chains. Compound 2 displays intense photoluminescence in the solid state at room temperature upon photo-excitation at 245 nm. The photoluminescence behaviors of the polymer 2 are related to the intraligand emission excited state.

A new three-dimensional non-interpenetrating coordination polymer, [{Cu(dps)2(SO4)}·3H2O·DMF]n (1) (dps=4,4′-dipyridyl sulfide) was synthesized and structurally characterized. 1 crystallizes in triclinic system, space group P−1 with cell parameters of a=10.9412(1) Å, b=11.8999(1) Å, c=12.5057(1) Å, V=1400.7(3) Å3, Z=2, Dc=1.573 g cm−3, F(0 0 0)=686, μ=1.059 mm−1. R1=0.0436, wR2=0.1148. In the polymeric architecture, SO42- serve as bridging coligands to connect highly puckered [Cu2(dps)2]n frameworks resulting in a 3D motif containing channels for guest molecule inclusion. Quantum chemistry calculation shows that the third-order NLO properties of polymer 1 are controlled by SO42- groups and dps ligands, and metal ions have less influence on the third-order NLO properties.Three-dimensional molecular network, [{Cu(dps)2(SO4)}·3H2O·DMF]n, and its different third-order NLO performance (dps=4,4′-dipyridyl sulfide).

A new nanocrystalline inorganic–organic hybrid semiconductor [(BV)2(Ag5Br9)]n (1) with an intriguing windmill-like 1-D [Ag5Br9]nn− polymeric chain was assembled. Great efforts were devoted to investigate its semiconducting properties and applications, such as photoluminescence, emission decay lifetime, waste water purification, electrochemistry behavior and dielectric properties.