3D Zinc Research Articles

An extended metallacrown architecture and an unusual 4.8 2 topology in a zinc metal-organic complex

A novel 2D zinc complex with unusual 4.8 2 topology, {[Zn 2(dpa) 2(bpp) 2(H 2O) 3] · 0.75(H 2O)} n , (H 2dpa = diphenic acid, bpp = 1,3-bis(4-pyridyl)propane) (1) was hydrothermally synthesized and structurally characterized. It has extended metallacrown architecture incorporating decorated regular 12-MC Zn(II)O(dpa)…O(dpa)-4 SBUs (secondary building units) which are further connected by the flexible bbp ligands to complete a 2D network. Fluorescent study of 1 shows that it has an emission at 425 nm in the solid state at room temperature.

Assembled bright green fluorescent zinc coordination polymer

A 1D zinc coordination polymer with bright green fluorescence, [Zn(4,4'-bipy)(H2O)4][Zn(4,4'-bipy)(1.5)(L)(H2O)2]2(L).6H2O (L = 4,4'-bis(2-sulfonatostyryl)biphenyl), has been designed, hydrothermally synthesized and characterized; the interesting structure consists of three types of infinite chain: a neutral sandwich-like chain, ionic and cationic chains.

Synthesis and single-crystal structure analysis of a new layered zinc phosphate

Abstract A new 2D zinc phosphate [H3NCH(CH3)CH2NH3]2+ 0.75[COOH(CH2)COOH]0.25(Zn3P3O11OH)2- * 0.5NH4 + consists of zinc phosphate layers, which are intercalated by diprotonated 1,2-diaminopropane, malonic acid, and NH4 + ions. The inorganic layers are composed of alternating ZnO4 and PO4 (PO3OH) tetrahedra that form 8-membered ring apertures. The intercalated species strongly interact with the zinc phosphate layers through hydrogen bonds, which is a key factor in stabilizing the structure. Crystal data: monoclinic, P21/a, a = 8.3457(1) Å, b = 16.8953(3) Å, c = 10.1817(2) Å, β = 95.3121(8)°, Z = 4, R = 0.0423.

Building three-dimensional metal phosphites from the corner-shared four-membered rings chain

Three new compounds, a one-dimensional (1D) zinc phosphite, (C 4H 8N 2H 4)[Zn(HPO 3) 2] ( I), two three-dimensional (3D) metal phosphites (C 4H 8N 2H 4)[Zn 3(HPO 3) 4] ( II) and (C 4H 8N 2H 4)[Zn (3− x) Co x (HPO 3) 4(H 2O) 2] ( x≈0.83) ( III) have been synthesized under hydrothermal conditions templated by piperazine and characterized by single-crystal X-ray diffraction, XRD, IR, UV-vis spectra and SQUID magnetometer. Compound I displays 1D chain-like structure, containing corner-shared (cs) four-membered rings. Interestingly, the structures of II and III show 1D chains similar to those observed in I. It is noteworthy that III represents the first cobalt-substituted zinc-phosphite. Crystal data: I, monoclinic, C2/ c, a=17.748(2) Å, b=7.428(9) Å, c=8.8071(11) Å, β=105.345(3)°, V=1091.9 Å 3, Z=4. II, Monoclinic P2 1/ c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å 3, Z=4, and III, Monoclinic P2 1/ c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å 3, Z=2.

A three-dimensional zinc(II) interpenetrating network and a π–π induced silver(I) zigzag complex connected by 1,3-di(imidazole-1-yl-methyl)-5-methylbenzene

A 3D zinc(II) threefold interpenetrating network {[Zn(dimb) 2](ClO 4) 2} n ( 1) and a π–π induced silver(I) double zigzag polymer {[Ag(dimb)](NO 3)·(H 2O)} n ( 2) were synthesized via a functional bidentate ligand 1,3-di(imidazole-1-yl-methyl)-5-methyl-benzene (dimb). The X-ray single crystal structural study indicated that the former complex represents an example of 3D interpenetrating network with a diamond topology in which aromatic ligands serve as the connector, while the latter is the first double zigzag polymer that has been formed by two adjacent infinite 1D zigzags through π–π interactions between benzene rings of the ligand.

Understanding the building-up process of three dimensional open-framework metal phosphates: acid degradation of the 3D structures to lower dimensional structures.

Acid degradation of 3D zinc phosphates primarily yields a one-dimensional ladder compound, an observation that is significant considering that the latter forms 3D structures on heating in water.

Thermally Stable Self‐assembling Open‐Frameworks: Isostructural Cs+ and (CH3)4N+ Iron Germanium Sulfides

AbstractHere we report on investigations that have revealed for the first time that the Cs+ ion templates the same metal germanium sulfide open‐framework as (CH3)4N+ (TMA+), and that metal complexing agents enhance crystal size by at least two orders of magnitude. The synthesis, structures and thermal properties of Cs2FeGe4S10 ·× H2O and TMA2FeGe4S10 are also described. Both have 3D zinc blende‐type open‐framework structures. These materials have the same connectivity as TMA2MnGe4S10. The tetrahedral sites in the lattice are alternately substituted by pseudo‐tetrahedral Fe2+ and adamantanoid Ge4S104‐ building blocks, covalently linked together by Fe(μ‐S)Ge bridge bonds, to give a tetragonal unit cell. The charge‐balance of the anionic framework [Fe‐Ge4S10]2‐ is maintained by either Cs+ or TMA+ ions in the cavity spaces. Synthesis of these materials demonstrates an interesting example of a self‐assembly process in which a 3D framework is built from molecular precursors. Water adsorption‐desorption cycling from room temperature to 200 °C reveals framework flexibility between larger and smaller tetragonal unit cell 14 isotypes. The compound TMA2FeGe4S10 is stable in nitrogen at 350 °C and under vacuum at 450 °C. The corresponding temperatures for Cs2FeGe4S10 are 530 °C and 630°C; it is stable on cooling to room temperature under vacuum, and after subsequent exposure to air. Six hundred thirty degrees celsius is the highest recorded temperature at which the integrity of a non‐oxide framework has been maintained. The framework stability and flexibility of “all‐inorganic” Cs2FeGe4S10 provides an encouraging example for researchers interested in developing sulfide‐based framework materials with practical applications.

Ab initio models for ZnS surfaces: the influence of cluster size on surface properties: II. Three-dimensional models

Models for zinc sulfide surfaces varying from 2D slabs to 3D zinc blende clusters containing several ZnS layers were studied. The energies and electronic properties are shown to converge monotonically as the model size increases. In some cases some size-dependent variation was found. The influence of edges and vacancies remains local, damping quickly beyond the neighboring atoms.