Jie-Hui Yu

Syntheses, characterization and optical properties of some copper(I) halides with 1,10-phenanthroline ligand

The hydrothermal reactions of CuX2 or CuX with phen (1,10-phenanthroline) have resulted in the syntheses of eight compounds 1–8. In these, 1∶1 adducts of CuX/phen are reported: ionic [Cu(phen)2][CuX2] (X=Cl 1, Br 2) and dimer [Cu2I2(phen)] 3; the trinuclear clusters [Cu3X3(phen)2] (X=Br 5, I 7) were first prepared and the structures can be best described as 1∶1 adducts of dimers and CuX; the chain compounds 6 and 8 belong to the same series with the formula [CuX2L] (L=organic ligand), but the chain arrangement is different; the structure of 4 is yet being refined. Compounds 1–8 have a high thermal stability. The third-order nonlinear optical properties of compounds 5, 6 and 8 were investigated and all exhibit a reverse saturable absorption (α2>0) and self-defocusing performance (n2<0).

Hydrothermal synthesis and characterization of a copper(I) halide coordination polymer with isonicotinic acid (IN) ligand as a template possessing three-dimensional supramolecular network structure

Abstract The title compound [CuBr(IN)]n 1 was hydrothermally synthesized from a simple reaction of CuBr2–IN–KBr–NaOH–H2O. X-ray analysis revealed that it is a new example containing extended one-dimensional staircase chain in copper(I) halide family. Its structure can be better described as a three-dimensional supramolecular network assembled via a combination of coordinate–covalent bonds and intermolecular hydrogen bonds. Moreover, compound 1 was characterized by elemental analysis, IR spectrum and TGA analysis.

New organically templated chained and layered iodoplumbates

In acidic alcohol/aqueous solution, simple solvo(hydro)thermal self-assembly between Pb(II) salts, KI and pip/dabco (pip = piperazine; dabco = 1,4-diazabicyclo[2,2,2]octane) created three new organically templated iodoplumbates as the chained [H2dppip][Pb2I6]·H2O 1 and [H2depip][Pb2I6]·H2O 2 and the layered [H2dabco][Pb3I8] 3 (dppip = N,N′-dipropylpiperazine; depip = N,N′-diethylpiperazine). Note that dppip/depip were derived respectively from the solvothermal in situ N-alkylation reactions of pip with ethanol/propanol in acidic KI solution. Ultraviolet-visible (UV-vis) spectrum analysis indicates that the three compounds are all potential semiconductor materials with energy gaps of 3.46 eV for 1, 3.02 eV for 2 and 3.31 eV for 3.

2D and 3D networks of lanthanide with mixed dicarboxylate ligands: syntheses, crystal structures and photoluminescent properties

A series of lanthanide complexes with mixed polycarboxylate ligands, [Ln2(op)2(ox)(H2O)4]n·nH2O (Ln = Ce, Pr, Nd, Sm, Eu and Gd for 1–6, respectively), [KLn(pma)1/2(ox)(H2O)]n (Ln = Tb (7) and Dy (8)), [KLn2(mp)3(ox)1/2(H2O)3]n (Ln = Ce(9) and Pr(10)) (op = o-phthalate, ox = oxalate, pma = pyromellitate and mp = m-phthalate), have been prepared, and their photoluminescent properties have been investigated. Compounds 1–6 show (3,4)-connected 2D network structures consisting of {Ln(op)}n staircase chains bridged by ox ligands. Compounds 7 and 8 consist of 1D zigzag {Dy(ox)}n chains linked by pma ligands adopting a new μ4-hexadentate coordination mode to form 2D 6-connected networks with (36·46·53) topology. Through K⋯O interactions, the 2D networks are further connected to construct 3D structures. Compounds 9 and 10 display inorganic–organic 3D topology networks with the Schlafli symbol (3·43·52)(32·410·59·614·7)(42·5) containing mixed (3,4,9)-connected nodes.

Organically templated chained chlorocadmates and cadmium-chloro thiocyanates

With the protonated piperazine (pip) and triethylenediamine (1,4-diazabicyclo[2,2,2]octane, dabco) as the templates, two chained chlorocadmates [H2pip][Cd2Cl6(H2O)2] 1, [H2dabco][Cd2Cl6]·H2O 2 and two chained cadmium-chloro thiocyanates [H2pip][CdCl3(SCN)]·2H2O 3, [H2dabco]2[Cd3Cl8(SCN)2]·H2O 4 were obtained, and characterized by IR analysis, CHN analysis, TG analysis and X-ray single-crystal diffraction. The 1-D chain structure of compound 1 is the simplest, and can be described as a zigzag infinite extension of Cd octahedra via sharing the edges. Compound 2 shows a double-chain structure, comprising the dinuclear Cd2Cl9 subunits linked together via sharing the corners and the edges. Compounds 3 and 4 are the first examples of a family of organically templated chained cadmium-chloro thiocyanates. Compound 3 shows a linear-chain structure, comprising the Cd2Cl6 dimers by the SCN−groups, whereas compound 4 shows a stepped-chain structure, comprising the hexanuclear Cd6Cl16 subunits by the SCN−groups. Through intramolecular and intermolecular hydrogen-bonded interactions, all the title compounds are self-assembled into the 2-D or 3-D supramolecular networks. The fluorescence spectra show that compounds 1–3 possess fluorescence properties with emission peaks around 370 nm.

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a novel one-dimensional copper(I) cyanide-organodiimine coordination polymer [Cu6(CN)6(phen)4]n (phen = 1,10-phenanthroline)

Abstract A novel one-dimensional chain coordination polymer [Cu 6 (CN) 6 (phen) 4 ] n 1 was synthesized from the simple hydrothermal reaction of Cu(CH 3 COO) 2 ·H 2 O, K 3 [Fe(CN) 6 ] and phen·H 2 O. With phen, CuCN exhibits a novel B–C–B–C chain array, namely the infinite chain is propagated via alternately three-coordinate (B) and four-coordinate (C) sites of monovalent Cu ions. It should also be noticed that the compound is the first example where the parent chain not only exhibits the [Cu(phen)] + side arm, but also is directly bound to the chelate ligand. Moreover, the third-order non-linear optical property of compound 1 was also investigated and it shows the reverse saturable absorption and self-focusing performance.

New thiocyanatocadmates with bidentate N-heterocyclic molecules as the templating agents: synthesis and structural characterization

The room-temperature reactions between CdX2, NH4SCN and bidentate N-heterocyclic molecules in acidic C2H5OH/H2O solutions yielded five new thiocyanatocadmates, [H2bpp][CdCl2(SCN)2] (bpp = 1,3-bis(4-piperidyl)propane) 1, [H2bpe][CdBr2(SCN)2] (bpe = 1,2-bis(4-pyridyl)ethane) 2, [H2(4,4′-dtdpy)][Cd2(SCN)6] (4,4′-dtdpy = 4,4′-dithiodipyridine) 3, [H2(4,4′-dtdpy)][CdBr2(SCN)2] 4 and [H(2,2′-dtdpy)][Cd(SCN)3] (2,2′-dtdpy = 2,2′-dithiodipyridine) 5. It is noteworthy that (i) in compound 3, Cd2+ and SCN− aggregate together to form two types of ribbons with H2(4,4′-dtdpy)2+ as the templating agent; (ii) in compound 5, 2,2′-dtdpy is monoprotonated, and the anion [Cd(SCN)3]− shows a 2D honeycomb-like layer structure; (iii) in compounds 1–4, the N-heterocyclic molecules still act as the linkers to extend the inorganic anions into 1D or 2D supramolecular networks via weak hydrogen-bonded interactions with piperidyl/pyridyl N atoms as the acceptors, although they are diprotonated. In ethanol solution, all of the title compounds emit light upon excitation.

Oxalate-extended Cd2+–acylhydrazidate coordination polymers: synthesis, structure and fluorescence property

Two new oxalate-propagated Cd2+–acylhydrazidate coordination polymers [Cd2(ox)0.5(Hpth)(pth)(bpy)2] (ox = oxalate, pth = phthalhydrazidate, bpy = 2,2′-bypyridine) 1 and [Cd2(ox)(pdh)2]·H2O (pdh = pyridine-2,3-dicarboxylhydrazidate) 2 were obtained by simple hydrothermal self-assemblies of Cd(CH3COO)2, aromatic dicarboxylic acids, N2H4, and oxalic acid with or without bpy. The acylhydrazidate molecules (pth, pdh) originated from the acylation of N2H4 with aromatic dicarboxylic acids. X-ray analysis revealed that in both compounds, ox acts as the second linker, extending the metal–acylhydrazidate oligomers (tetranuclear for 1; dinuclear for 2) into the high-dimensional coordination polymers. In compound 1, the monoacylhydrazidate molecule with a −2 oxidation state was observed for the first time. In the solid state, only compound 2 emits light, while in an aqueous solution, both compounds emit light. The density functional theory (DFT) calculations indicate that whether in the solid state or in an aqueous solution, the emissions for compound 2 are both assigned to the charge transfer within the pdh molecule, corresponding to the charge transfer from the π* orbitals of the pyridine ring moiety to the π orbitals of the acylhydrazidate ring moiety. The solvent effect of water causes the blue shift from 525 nm to 405 nm. The blue-light emission (465 nm) for compound 1 in an aqueous solution is assigned to the charge transfer between the pth molecules, corresponding to the charge transfer from the π* orbitals of the benzene ring moiety of one pth molecule to the π orbitals of the acylhydrazidate ring moiety of another pth molecule. The Cd2+ center provides the path for charge transfer.

Synthesis, structural characterization and photoluminescence property of four di(mono)acylhydrazidate-coordinated Cd2+ and Zn2+ compounds

Under hydrothermal conditions, the simple reactions between metal salts, aromatic polycarboxylic acids (4,4′-diphthalic anhydride ketone, dphahk; 4,4′-sulfoyldiphthalic anhydride, sdpha; pyridine-2,3-dicarboxylic acid, pdca) and N2H4·H2O with or without the presence of phenanthroline·H2O (phen) yielded four di(mono)acylhydrazidate-coordinated Cd2+/Zn2+ compounds as [Cd(DPHKH)(phen)]·1.75H2O 1, [Zn3(DPHKH)2(HDPHKH)2(phen)2]·8H2O 2, [Cd(SDPTH)(phen)(H2O)]·H2O 3 and [Zn(PDH)2(H2O)2] 4 (DPHKH = 4,4′-diphthalhydrazidatoketone hydrazone; SDPTH = 4,4′-sulfoyldiphthalhydrazidate; PDH = pyridine-2,3-dicarboxylhydrazidate). The di(mono)acylhydrazide molecules in the title compounds originated from the hydrothermal in situ acylation reactions of aromatic polycarboxylic acids with N2H4·H2O. It is noteworthy that another kind of hydrothermal in situ reaction was also observed when preparing compounds 1 and 2, namely the nucleophilic addition reaction between the keto group (of dphahk) and N2H4. The photoluminescence analysis indicates that the compounds in the different states (in the solid state or in aqueous solution) may exhibit different emission behaviors.

Structural characterization of a series of new organically templated chained thiocyanato(halo)cadmates

The room-temperature self-assemblies between CdX2, NH4SCN and organic N-heterocyclic/diamine molecules in acidic C2H5OH/H2O solutions produced six organically templated chained thiocyanato(halo)cadmates [H2bp][CdCl2(SCN)2] 1, [H2bp][Cd(SCN)4] 2, [H2bpp][Cd3Br(SCN)7] 3, [H2bpy][CdBr2(SCN)2] 4, [H2bpe][Cd(SCN)4] 5 and [H2dach][CdCl4] 6 (bp = 4,4′-bipiperidine; bpp = 1,3-bis(4-piperidyl)propane; bpy = 4,4′-bipyridine; bpe = 1,2-bis(4-pyridyl)ethane; dach = 1,4-diaminocyclohexane). Although the organic N-heterocyclic/diamine molecules are diprotonated, they still act as the bridges to extend the inorganic anionic chains into 2-D or 3-D supramolecular networks via the weak hydrogen-bonded interactions with N atoms as the donors/acceptors.