Simultaneous Growing of Two New Cd(II) Metal–Organic Frameworks with 2,6-Naphthalendicarboxylic Acid as New Precursors for Cadmium(II) Oxide Nanoparticles: Thermal, Topology and Structural Studies

Crystal structure and thermal stability of two new 3D Cd(II) metal–organic frameworks (MOF) containing 2,6-naphthalenedicarboxylate, [Cd(NDC)(DMF)], 1, and [Cd₃(NDC)₄], 2 (H₂NDC = 2,6-naphthalenedicarboxylic acid; DMF = N,N-dimethylformamide) have been studied. These two MOFs grow simultaneously within the same solution to give multiple crystals that are due to the general lability of Cd(II) complexes. Structure 1 shows a 3D neutral metal–organic framework with PtS topology and crystallizes in the triclinic system, space group P-1 (No. 2), whilst 2 crystallizes in the orthorhombic system, space group Fdd2 (No. 43) with body-centered cubic bcu-(4²⁴.6⁴) topology. The elongated nature of NDC results in large cavities in both compounds; however, the pores are filled by coordinated DMF molecules in 1. The thermal stability of 1 and 2 were studied by thermogravimetry and show stability to 400 °C for 1 and continuous weight loss for 2. CdO nanoparticles were prepared by direct calcination of 1 and 2 at 600 °C. The CdO nanoparticles were characterized by X-ray powder diffraction and its morphology were studied by scanning electron microscopy. The results show that the CdO is pure and has a uniform morphology.     

Synthesis of a New Interpenetrated Mixed Ligand Ni(II) Metal–Organic Framework: Structural, Thermal and Fluorescence Studies and its Thermal Decomposition to NiO Nanoparticles

Reaction of terephthalic acid and pyrazine with nickel nitrate under hydrothermal conditions forms a 3D metal–organic framework with the composition of [Ni(μ₃ ? tp)(μ₂ ? pyz)]_n (1), where H₂tp = 1,4-benzenedicarboxylic acid (terephthalic acid) and pyz = pyrazine. X-ray single crystal analysis reveals that Ni(II) centers adopt a distorted octahedral geometry which are surrounded by four oxygen atoms from three tp groups and two nitrogen atoms of pyrazine molecules in equatorial and axial positions, respectively. Coordination of Ni(II) centers by terephthalate linkers in ac plane forms infinite (4, 4)-connected 2D layers, which are further joined together by pyrazine groups to form an interlocked 3D structure. Topological studies show a two-fold interpenetrated uninodal 3D network with point symbol of (4¹²·6³). The polymer shows a blue emission band at 467 nm in the solid state at room temperature. The X-ray power diffractions (PXRD) and thermal gravimetric analysis of 1 are also presented and discussed. NiO nanoparticles have been prepared via direct calcination of 1 at 600 °C, with sizes of about 35–45 nm. Nanoparticles were further characterized by IR, scanning electron microscopy equipped with energy dispersive X-ray analyses and PXRD technique.     

Synthesis and Characterization of New Cobalt(II)–Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination,DFT Calculation and Spectroscopic Studies

The new 2-D cobalt(II) coordination polymer with pyrazine was synthesized surprisingly from reaction of CoCl₂ and tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine (tpphz) in methanol as medium and characterized by means of Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and X-ray single crystal analysis. The results showed that coordination polymer consist of cobalt(II) chain with pyrazine-bridged which crystallizes in orthorhombic unit cell (a?=?10.1307, b?=?10.1310, c?=?10.6838 Å) and space group Pban. Density functional theory (DFT) calculations were also done to figure out the electronic structure of the compound from theoretical aspect. The electronic spectrum of coordination polymer was investigated and the DFT/TDDFT procedures were employed to assign the absorption bands. The thermal decomposition of the title compound resulted in formation of cobalt(II) oxide nanoparticles with average size of 50 nm.     

Synthesis and Characterization of New Metal–Organic Frameworks Based on Tetracyanoplatinate(II) and N,N′-bis(2-hydroxyethyl)ethylenediamine: Single Crystal Structures of ZnII and CdII Complexes Along with Magnetic Properties of NiII and CuII Complexes

Characterization and synthesis of novel cyano bridged coordination compounds [Ni(bishydeten)Pt(CN)₄] (1), [Cu(bishydeten)Pt(CN)₄] (2), [Zn(bishydeten)Pt(CN)₄] (3), [Cd(bishydeten)Pt(CN)₄] (4) [bishydeten = N,N′-bis(2-hydroxyethyl)ethylenediamine (C₆H₁₆N₂O₂)] were reported herein. The IR spectra of these coordination compounds verified the formation of aforementioned complexes. The ground state of the paramagnetic electron in the Cu^II located in tetragonal distorted octahedral sites (D _4h ) was found to be d_x2−y2 for complex 2. As for complex 1, an EPR signal was not observed because of diamagnetic property of the Pt^II and momentary relaxation times of the Ni^II. All complexes followed identical decomposition mechanism in thermal analysis and thermal stabilities of complexes changed in the order of 1 > 4 > 3 > 2. Both 3 and 4 exhibit polymeric structure according to X-ray single structure analysis. While bishydeten coordinated with three donor atoms (N,N′, and O) in complex 3, it acts as a bidentate ligand (N, and N′) in complex 4. Magnetic properties of complexes 1–2 at 15–300 K temperature range were determined as antiferromagnetic with Weiss constants = −2.619 and −0.847 K respectively.     

The Role of Weak Intermolecular Interactions in the Assembly of a Series of d<Superscript>10</Superscript> Metal Coordination Polymers Based on <Emphasis Type="Italic">N,Nʹ</Emphasis>-Bis-Pyridin-3-Ylmethylene-Naphtalene-1,5-Diamine Ligand; Ultrasonic Synthesis,Spectroscopic and Structural Characterization

The motivation of this work is to highlight factors that influence the supramolecular structures of d¹⁰ metal coordination polymers. Two novel Hg(II) and Cd(II) 1D coordination polymers (CPs) have been constructed from metal iodide and a N,N′-bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand using conventional methods. Our analyses reveal the substantial role of weak hydrogen bonds and π–π stacking interactions in the assembly of these series of compounds. These compounds were studied using X-ray crystallography, infrared spectroscopy and X-ray powder diffraction. The supramolecular structures of these two compounds were compared with two structures that have been published recently. These coordination polymers in nano-size were synthesized under ultrasonication and their morphology were characterized using scanning electron microscopy (SEM).     

Preparation of a Novel Nano-scale Lead (II) Zig-Zag Metal–Organic Coordination Polymer with Ultrasonic Assistance: Synthesis,Crystal Structure,Thermal Properties,and NBO Analysis of [Pb(μ-2-pinh)N<Subscript>3</Subscript> H<Subscript>2</Subscript>O]<Subscript>n</Subscript>

A novel nano-cauliflower-shaped lead(II) metal–organic coordination polymer, [Pb(μ-2-pinh)N₃ H₂O]_n (1), was synthesized using an ultrasonic method. The nanostructure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction, IR spectroscopy, elemental analysis, and thermal analysis. The compound was structurally characterized by single-crystal X-ray diffraction. The coordination compound takes the form of a zig-zag one-dimensional polymer in solid state. The coordination number of the lead(II) ions is six (PbN₄O₂) with three nitrogen atoms and one oxygen atom from two linker organic ligands, as well as one oxygen from coordinated water and one nitrogen atom from terminal coordinated azide anion. It has a stereo-chemically active lone electron pair, and the coordination sphere is hemidirected. The zig-zag 1D chains interact with neighbouring chains through weak interactions, creating a 3D supramolecular metal–organic framework. Lead oxide nanoparticles were obtained by thermolysis of the new nano coordination compound at 180 °C with oleic acid as a surfactant. The morphology and size were further studied using SEM. Natural bond orbital analyses demonstrate the electronic properties of the lead centre and other atoms.