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The manipulation of structures and properties is a useful method in designing new materials. In this paper, two organic–inorganic hybrid compounds [(C6H15ClNO)2CoX4] (1, X = Cl; 2, X = Br) with reversible phase transition characteristics have been successfully synthesized. Systematic characterizations including crystal structure, thermal, dielectric, semiconducting, and photoluminescence properties were performed. Replacement of Cl with Br brings about not only the variation of the space group from C2/c to P21/c but also their properties. In comparison with Cl, the large Br atom could slow down the phase transition dynamics and give a larger thermal hysteresis of ∼25 K. Consequently, different shapes of switchable dielectric transition behavior are shown between 1 and 2. In addition, compound 2 has a smaller semiconducting band gap Eg than 1 (1.60 vs 1.65 eV). The results of this study will provide positive clues to manipulate the property of organic–inorganic hybrid compounds.

Organic–inorganic hybrid metal halides with temperature-triggered responsive switchable dielectric properties have evoked great attention for their potential application in the field of optoelectronic information. Here, we present a new organic–inorganic hybrid metal halide switchable dielectric material, [(C3H5)2N(CH3)2]2SnCl6 (1), which is obtained by the reaction of diallyldimethylaminium chloride and tin(IV) chloride pentahydrate. Compound 1 exhibits excellent high-temperature switchable dielectric performance and antifatigue. Notably, 1 also exhibits multifunctionality with semiconducting and photoluminescence property. Such a Sn(IV)-based organic–inorganic hybrid with outstanding switchable dielectric, semiconducting, and photoluminescence characteristics will pave a new approach in the development of Sn(IV)-based metal halides with practical applications.

A series of novel 4f-3d crystalline porphyrinic compounds, {[Co(TPPS)]2[Ln(Histidine)(H2O)][Ln(H3O)3]}n·nH2O (Ln = Sm (1), Eu (2), Dy (3); TPPS = 5,10,15,20-tetra(4-sulfonatophenyl)porphyrinato) with TPPS and histidine as mixed ligands, have been prepared and characterized by single-crystal X-ray diffraction technique. Complexes 1–3 are isomorphous and characteristic of a three-dimensional (3D) framework with the lanthanide ions in two kinds of coordination geometries, i.e., eightfold square antiprism and ninefold monocapped square antiprism. The porphyrin macrocycles adopt a saddle-distorted nonplanar conformation with an embedded cobalt ion binding to four pyrrole nitrogen atoms. As revealed by the photoluminescence measurement, they exhibit blue emission. Variable-temperature magnetic susceptibility reveals that complexes 1–3 are antiferromagnetic. Their FTIR, CV, DPV, and UV/vis results are also studied in detail.

We report a new flexible switchable dielectric composite film toward practical application in devices based on β-phase-dominated PVDF modified with single-protonated 1,4-diazabicyclo[2.2.2]octane fluoborate (DabcoHBF4). Our study suggested that incorporating polar molecular filler (DabcoHBF4) into β-phase-dominated PVDF is an effective method to fabricate switchable dielectric thin film, which could avoid sophisticated operation in cultivating bulk crystals of molecular materials. The composite film with 40% of DabcoHBF4 (0.40BF) could exhibit large dielectric change between high and low dielectric states comparable to that of pure DabcoHBF4 at phase-transition temperature. We postulated that the excellent switchable dielectric property of 0.40BF was attributed to the induced orientation alignment of β-phase-dominated PVDF and dielectric confinement effect.

Two new zinc compounds, [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1) and [Zn(phtz)(nic)]2n (2) (Hmtz = 5-methyltetrazole, Hphtz = 5-phenyltetrazole, Hnic = nicotinic acid), have been synthesized by a dual-ligand approach under solvothermal conditions. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy, respectively. The X-ray diffraction analysis reveals that both compounds exhibit a noncentrosymmetric polar packing arrangement. Compound 1 is a 3D framework constructed from the zigzag chain subunits of [Zn(nic)]+ with a 4-connected “irl” topology. Compound 2 possesses a 2D 4-connected ‘“sql” topology constructed from the linear chain subunit of [Zn(nic)]+, which are linked together with phtz– ligands. Impressively, both of the two compounds display second-harmonic generation response and ferroelectric behaviors. Furthermore, the photoluminescence of the compounds was also investigated.

The self-assembly reactions of Ln(NO3)3·aq (Ln = La, Nd, Sm, Gd, Dy, Er, and Yb) with K3[Fe(CN)6] and three monosulfoxide ligands, dimethylsulfoxide (DMSO), diethylsulfoxide (DESO), and tetramethylene sulfoxide (TMSO), respectively, in water give rise to three series of 21 LnIII−FeIII complexes with ten kinds of compositions and structures: cis-[Fe(CN)4(μ-CN)2La(H2O)3(DMSO)3]n·nH2O (1), [Fe(CN)5(μ-CN)Ln(H2O)3(DMSO)4]·H2O [Ln = Nd (2), Dy (5)], [Fe(CN)5(μ-CN)Ln(H2O)4(DMSO)3]·H2O [Ln = Sm (3), Gd (4)], trans-[Fe(CN)4(μ-CN)2Ln(H2O)(DMSO)4]n [Ln = Er (6), Yb (7)], [Fe(CN)6][La(H2O)6(DESO)3] (8), trans-[Fe(CN)4(μ-CN)2Ln(H2O)4(DESO)2]n·2nH2O [Ln = Nd (9), Sm (10), Gd (11), Dy (12), Er (13)], cis-[Fe(CN)4(μ-CN)2Yb(H2O)3(DESO)2]n·2nH2O (14), [Fe(CN)5(μ-CN)Ln(H2O)3(TMSO)4]·1.5H2O [Ln = La (15), Nd (16), Gd (18)], cis-[Fe(CN)4(μ-CN)2Sm(H2O)4(TMSO)2]n (17) and cis-[Fe(CN)4(μ-CN)2Ln(H2O)3(TMSO)2]n·nH2O [Ln = Dy (19), Er (20), Yb (21)]. The X-ray structure analyses show that 2−5, 15, 16, and 18 have cyano-bridged dinu...

Ten compounds of the IIB metal halide/pseudohalide-bipy system, β-[ZnBr2(4,4‘-bipy)]n (1), [Cd2Br5(4,4‘-bipyH)2](CdBr3) (2), [Cd3Br6(4,4‘-bipy)]n (3), [CdI2(4,4‘-bipy)]n (4), (HgI2)2(4,4‘-bipy) (5), [Hg(CN)2(4,4‘-bipy)(H2O)2]n (6), HgCl2(2,2‘-bipy) (7), [HgCl2(2,2‘-bipy)]·2HgCl2 (8), [Hg3Br6(2,2‘-bipy)]·HgBr2 (9), and [HgI2(2,2‘-bipy)]·HgI2 (10), have been synthesized via hydro(solvo)thermal and solid-state reactions; except for 4, all the other compounds are reported for the first time. Compound 1 features a 1-D zigzag chain, based on tetrahedral zinc atoms bridged by 4,4‘-bipy molecules and terminally coordinated by two bromine atoms. The chains are linked by hydrogen bonds and π···π interactions to form a 2-D sheet. Compound 2 possesses dinuclear [Cd2Br5(4,4‘-bipyH)2]+ cations and CdBr3- anions. Compound 3 has a 2-D layered structure, constructed from novel triple chains and bridging 4,4‘-bipy ligands. The triple chains contain edge-shared CdBr6 and CdBr5N octahedra. In 4, the layers are formed by mono...

The incorporation of [Mn(2,2‘-bipy)2]2+ with thioarsenate resulted in the formation of two novel compounds, [Mn3(2,2‘-bipy)3(AsVS4)2]n·nH2O (1) and Mn2(2,2‘-bipy)As2IIIS5 (2), in which the main-group chalcogenide framework is incorporated with a [tm(2,2‘-bipy)m]n+ complex. Meanwhile, the tetrathioarsenate(V) anion acts as a new μ3-1κS:1,2κS‘:2,3κS‘ ‘:3κS‘ ‘‘ ligand in 1, in which all four S atoms of the [AsVS4]3- anion are coordinating to metal. As a result, the two compounds exhibit semiconducting properties (Eg = 2.18 eV (1) and 1.83 eV (2)) and strong blue photoluminescence, with the emission maximum occurring at about 440 nm. Magnetic measurements show that both compounds have AF ordered states with Neel temperatures of 19 and 24 K for 1 and 2, respectively.

Four cyano-bridged 4f−3d (lanthanide−transition metal) bimetallic assemblies, [Sm(DMF)2(H2O)3(μ-CN)3M(CN)3]n·nH2O (M = Fe (1), Co (2)) with 2-D monolayered structures and [Sm(DMF)(H2O)3(μ-CN)4M(CN)2]n·nH2O (M = Fe (3), Co (4)) with 2-D bilayered structures (DMF = N,N-dimethylformamide), were rationally prepared by a facile approach, a ball-milling method, and characterized by X-ray diffraction studies and magnetic measurements. The unprecedented 2-D bilayered 4f−3d hexacyanometalates (3 and 4) were obtained by controllably reducing the half amount of DMF in the reactive system in comparison with 1 and 2 through a ball-milling method.

Two series of novel complexes, [Ln(dca)2(Phen)2(H2O)3](dca)·(phen) (Ln = Pr (1), Gd (2), and Sm (3), dca = N(CN)-, phen = 1,10-phenanthroline) and [Ln(dca)3(2,2‘-bipy)2(H2O)]n, (Ln = Gd (4), Sm (5), and La (6), 2,2‘-bipy = 2,2‘-bipydine), have been synthesized and structurally characterized by X-ray crystallography. The crystal structures of the first series (1−3) are isomorphous and consist of discrete [Ln(dca)2(Phen)2(H2O)3]+ cations, dca anions, and lattice phen molecules; whereas the structures of the second series (4−6) are characterized by infinite chains [Ln(dca)3(2,2‘-bipy)2(H2O)]n. The Ln(III) atoms in all complexes are nine-coordinated and form a distorted tricapped trigonal prism environment. The three-dimensional frameworks of 1−6 are constructed by intermolecular hydrogen bond interactions. Variable-temperature magnetic susceptibility measurements for complexes 1, 2, 4, and 5 indicate a Curie−Weiss paramagnetic behavior over 5−300 K.

The self-assembly of LiBr and bis(diphenylphosphineoxo)ethane (dppe-O) in tetrahydrofuran (THF) and further diffusion with n-pentane gave rise to a new coordination polymer formulated as [Li 2 (dppe-O) 3 Br 2 ] n and has been shown by X-ray diffraction analysis to be a 2-D noninterpenetrating honeycomb-like layer of (6,3) topology containing 42-membered rings with 1-D hydrophobic channels. These 2-D layers stack together tightly through weak hydrogen bonding and strong π...π stacking interactions to form a 3-D nanoporous structure.