Zhi-Rong Chen

Rigidity/flexibility competition in organic/iodoargentate hybrids: a combined experimental and theoretical study

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.

Incorporating a Transition Metal Complex into Polymeric Iodoplumbate: Structure Characterization, Properties and Theoretical Study of a Unprecedented Hybrid Semiconductor: {[Cu(en)2][Pb2I6]}n

A hybrid semiconductor {[Cu(en)2][Pb2I6]}n (1) (en = ethylenediamine) templated by a transition metal complex was synthesized and structurally characterized. The title compound consists of discrete structure-directing molecules (transition metal complex) and an inorganic iodoplumbate polymer. The iodoplumbate polymer could be described as a three-dimensional network constructed from a [Pb2I8]n4– double chain bridged by iodine. [Cu(en)2]2+ structure-directing cations are discrete, and interact with the inorganic moiety by strong static attraction and the H-bond of N–H···I to give a so-called hybrid structure. Experimental and theoretical optical property investigations indicate that 1 possesses semiconductor properties. A density functional theory calculation was executed to probe the regulation effect on the introduction of a second metal.

An organic–inorganic hybrid heterobridging luminescent copper(I) polymer exhibiting thermochromic behavior

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.

A 2-D framework incorporating lanthanide metal complex linkers into polymeric iodoplumbate

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.

Synthesis, Characterization, and Electronic Structures of Organically Templated Lead Halides with One- and Two-Dimensional Hybrid Structures, [(nbq)(PbI3)]n and {[(CH3)3NC2H4N(CH3)3]3(Pb6I18)}n

Two new organically templated lead(ii) iodide complexes, [(nbq)(PbI3)]n 1 and {[(CH3)3NC2H4N(CH3)3]3(Pb6I18)}n 2, have been synthesized in the presence of aromatic and aliphatic quaternary ammonium compounds, N-(n-butyl)quinolinium (nbq+) and [(CH3)3NC2H4N(CH3)3]2+, respectively, acting as structure-directing agents. Both 1 and 2 consist of uncoordinated structure-directing agents and inorganic moieties bound to the organic structure-directing agents. In 1, an inorganic (PbI3–)n one-dimensional polyanion chain is built up by face-sharing of distorted PbI6 tetrahedra. The inorganic framework of 2 presents a two-dimensional arrangement that could be discussed in terms of [Pb3I10]4– building blocks. Static attractive interactions between organic countercations and inorganic moieties were revealed through the crystal packing. Density functional theory calculations indicate that 1 possesses semiconductor properties, tuned by the π-electrons of nbq+. In contrast, 2 is conductive in the direction of aliphatic quaternary ammonium moiety.

Introducing p-block metals into iodoargentates: structures and properties of two new heterometallic hybrids

Two new heterometallic complexes, [Bi(phen)I4Ag(phen)] n (1) and [Pb(bipy)Ag3I5] n (2) (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine), have been synthesized, significant for incorporation of heavy p-block metals (Pb and Bi) into iodoargentate frameworks to get heterometallic complexes. Complex 1 could be described as the combination of Ag(phen)I4 and Bi(phen)I4 octahedra by edge-sharing and 2 is constructed from and [Pb(2,2′-bipy)]2+ by Pb–I covalent bonds. Their optical band gaps, fluorescences, and thermal behaviors are also discussed.

Preparation and Characterization of Two Bismuth(III) Iodide Inorganic/Organic Hybrid Solids

Two new organic/bismuth(III) iodide hybrids have been synthesized by a solution process, and their crystal structures were determined by an x-ray diffraction method. The first one, (EMP)3(Bi2I9) (EMP+ = N-ethyl-4-methyl-pyridinium) (1), crystallizes in the monoclinic system, space group P21/c, with M r = 3838.20, a = 19.945(4), b = 12.636(3), c = 20.327(4) Å, β = 118.82(3)°, V = 4488.4(16) Å3, Z = 2, D c = 2.840 g/cm3, F(000) = 3358, μ(MoKα) = 14.039 mm−1, the final R = 0.0678, and wR = 0.1676 for 7272 observed reflections with I > 2σ(I). The second, [(Phendione)BiI4]·(Phendione-H)·C2H5OH (Phendione = 1,10-phenathroline-5,6-dione) (2), belongs to the monoclinic system, space group C2/c, with M r = 1183.02, a = 37.254(8), b = 8.1776(16), c = 22.318(5) Å, β = 111.38(3)°, V = 6331(2) Å3, Z = 8, D c = 2.842 g/cm3, F(000) = 4296, μ(MoKα) = 9.511 mm−1, the final R = 0.0526, and wR = 0.1050 for 6555 observed reflections with I > 2σ(I). Compound 1 contains halobismuthate dimers, and it is noteworthy that the dimers and its organic countercations connect with each other by C–H···I hydrogen bonds to form a layered structure. Compound 2 is composed of [(Phendione)BiI4]− anions and Phendione-H+ cations, and hydrogen bonds contribute to give a one-dimensional (1-D) chain. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.17 and 1.93 eV, respectively.

Synthesis, Properties, and Theoretical Study of a Cation-Induced Iodoargentate Hybrid: [(PIP-H2)4·(Ag4I12)·H2O] n

A new cation-induced hybrid iodoargentate, [(PIP-H2)4·(Ag4I12)·H2O] n (1) (PIP = piperazine) has been obtained by the routine synthetic reaction in DMF solution and structurally determined. 1 crystallizes in monoclinic system, space group P21/n with unit cell parameters: a = 12.718(3), b = 9.3861(19), c = 20.098(4)Å, β = 90.33(3)°, V = 2399.1(8)Å3, Z = 4, C8H24Ag2I6N4O, M r = 1169.45, D c = 3.238 g/cm3, F(000) = 2080, μ(MoKα) = 9.356mm−1, the final R 1 = 0.0681 and wR = 0.1757 for 5255 observed reflections with I > 2σ(I). In 1, 0-D [Ag4I12]8− clusters were constructed from four vertex-sharing AgI4 tetrahedra and further linked by hydrogen bonds to give a 2-D layer. Luminescence can be detected in the title compound. Quantum chemistry calculation with DFT method was carried out to reveal its electronic structure.

Structure and property variations of lead iodide–organic coordination polymers tuned by substituted groups on phenanthroline

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 ligands 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.

Structural diversities of squarate-based complexes: photocurrent responses and thermochromic behaviours enchanced by viologens

By using squarates as coordination building units, six new complexes formulated as [Mg(C4O4)(H2O)2]n (1), [Pr2(C4O4)2(OA)(H2O)4]n (2), [Eu2(C4O4)3(H2O)8]n (3) [Cd2(C4O4)2(bpdo)(H2O)4]n (4), [Cd(C4HO4)2(H2O)4]·(MV)2·(C4O4)2 (5), and [Cd(C4HO4)2(H2O)4]·(EV)·(C4HO4)2 (6), where (C4O4)2− = squarate, OA = oxalic acid, MV = methyl viologen, EV = ethyl viologen, and bpdo = 4,4′-dipyrdiyl-N,N′-dioxide, have been synthesized under hydro/solvothermal conditions. They present structural dimensions from 3-D networks (1, 2), 2-D layers (3, 4) to 0-D clusters (5, 6) based on the versatile bridged modes of squarates and the introduction of second ligands. In particular, 5 and 6 are the first examples incorporating squarates (electronic-rich species) with viologens (electronic-poor species) in one lattice. Consequently, they exhibit not only photocurrent responses but also reversible thermochromism, which will be beneficial for the design of multi-functional materials.