Direct Synthesis of PbO Nanoparticles From a Lead(II) Nano Coordination Polymer Precursor: Synthesis,Crystal Structure,and DFT Calculations of [Pb2(dmp)2(μ‐N3)2(μ‐ClO4)2]n with the First Pb2‐(μ‐ClO4)2 Unit

Nanostructures of a new coordination polymer of divalent lead with the ligand 2, 9‐dimethyl‐1, 10‐phenanthroline (dmp) containing the first Pb₂‐(μ‐ClO₄)₂ motif, [Pb₂(dmp)₂(μ‐N₃)₂(μ‐ClO₄)₂]_n ( 1 ), was synthesized by a sonochemical method that produces the coordination polymers at nano size. The new nanostructure was characterized by scanning electron microscopy, X‐ray powder diffraction, IR, ¹H NMR and ¹³C NMR spectroscopy, and elemental analysis. Compound 1 was structurally characterized by single‐crystal X‐ray diffraction and the single‐crystal X‐ray data shows that the coordination number of Pb^II ions is six, (PbN₄O₂), with two N‐donor atoms from aza‐aromatic base ligands and four O‐donors from two perchlorate anions and two N‐donors from two azide anions. It has a “stereo‐chemically active” electron lone pair, and the coordination sphere is hemidirected. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π–π stacking interactions creating a 3D framework. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are in agreement with the crystal structure. The PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 23 nm. The morphology and size of the prepared PbO samples were further observed using SEM.     

Syntheses and Characterization of Mixed‐Anions Lead(II) Complexes, [Pb(phen)2(CH3COO)]X (X=NCS—, NO3— and ClO4—), Crystal Structure of [Pb(phen)2(CH3COO)](ClO4)

The 1:2 adduct lead(II) complexes with 1, 10‐phenanthroline (phen) containing three different anions, [Pb(phen)₂(CH₃COO)X] (X=NCS^—, NO₃^— and ClO₄^—), have been synthesized and characterized by CHN elemental analysis, IR‐, ¹H‐ and ¹³C NMR spectroscopy. The structure of [Pb(phen)₂(CH₃COO)(ClO₄)] was determined by single crystal X‐ray analysis. The Pb atom of the monomeric complex is coordinated by four nitrogen atoms of two 1, 10‐phenanthroline ligands and two oxygen atoms of the acetate ligand to form an irregular octahedron. The arrangement of the 1, 10‐phenanthroline and acetate ligands, exhibits a coordination gap around the Pb^II ion, possibly occupied by a stereochemical electron active lone pair on lead(II), which results in a hemidirected lead compound. The π‐π stacking interaction between the parallel aromatic rings may help to increase the coordination ‘gap’ around the Pb^II ion.     

Synthesis and Crystal Structure of a Novel Polymeric Lead(II) Compound: [Pb2(phen)2(N3)3(ClO4)]n

A 2D lead(II) coordination polymer [Pb₂(phen)₂(N₃)₃(ClO₄)]_n,( 1 ) containing 1,10‐phenanthroline (phen) and two different anions, has been synthesized and characterized by elemental analysis, IR and ¹H NMR spectroscopy and X‐ray crystallography. The single‐crystal X‐ray data show two different kinds of Pb²⁺ ions with coordination numbers of eight, Pb1 = PbN₆O₂ and Pb2 = PbN₈, with hemidirected and holodirected structures, respectively. The supramolecular features in 1 is negiotated through the weak but directional C‐H···O and C‐H···N interactions and aromatic π–π stacking interactions.     

Synthesis and Spectroscopic Characterization of New Lead(II) Thiosaccharinates. Molecular Structure of Bis(thiosaccharinato)tetrakis(pyridine)dilead(II) and Thiosaccharinato‐bis(1,10‐phenantroline)lead(II) Thiosaccharinate

Four new lead(II) thiosaccharinate complexes: [Pb(tsac)₂H₂O] (1) (tsac: thiosaccharinate anion), [Pb₂(tsac)₄(py)₄] (2) (py: pyridine), [Pb(tsac)(o‐phen)₂](tsac)·CH₃CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)₂(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus.     

Sonochemical Synthesis of a Novel Nanoscale Lead(II) Coordination Polymer: Synthesis,Crystal Structure,Thermal Properties,and DFT Calculations of [Pb(dmp)(μ‐N3)(μ‐NO3)]n with the Novel Pb2(μ‐N3)2(μ‐NO3)2 Unit

A new nanostructured coordination polymer of divalent lead with the ligand 2,9‐dimethyl‐1,10‐phenanthroline (dmp), [Pb(dmp)(μ‐N₃)(μ‐NO₃)]_n ( 1 ), was synthesized by sonochemical methods. The polymer was characterized by scanning electron microscopy, X‐ray powder diffraction, IR, ¹H NMR, and ¹³C NMR spectroscopy, and elemental analyses. Compound 1 was structurally characterized by single‐crystal X‐ray diffraction. The single‐crystal analysis shows that the coordination number of Pb^II ions is seven, (PbN₄O₃) has a “stereo‐chemically active” electron lone pair, and the coordination sphere is hemidirected. The chains interact with each other through π–π stacking interactions to create a 3D framework. The structure of the title complex was optimized by density functional calculations. The calculated structural parameters and the IR spectrum of the title complex are in agreement with the crystal structure.     

Synthesis and Structural Characterization and Thermal Properties of a Novel Aza‐aromatic Base Adduct of Cadmium Thenoyltrifluoroacetonate: A precursor for Pure Phase Nano‐sized Cadmium(II) Oxide

A novel aza‐aromatic base adduct of cadmium(II) thenoyltrifluoroacetonate, [Cd(phen)(ttfa)₂] ( 1 ), (phen = 1, 10‐phenanthroline; ttfa = thenoyltrifluoroacetonate) was synthesized and characterized by elemental analysis, IR, ¹H NMR, and ¹³C NMR spectroscopy, thermal analysis as well as X‐ray crystallography. The single‐crystal structure of this complex shows that the coordination number of the Cd²⁺ ions are six with two nitrogen donor atoms from aza‐aromatic base ligands and four oxygen donors from two thenoyltrifluoroacetonate ligands. The supramolecular features in these complexes are directed by weak directional intermolecular interactions. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are in agreement with the crystal structure. The CdO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average size of the nanoparticles was estimated by the Scherrer equation with the diameter about 45 nm. The morphology and size of the prepared CdO samples were further observed using SEM.     

Synthesis and Characterization of a New Thallium(I) Coordination Polymer of Tetrazolate Ligand as Precursor for Preparation of Thallium(III) Oxide Nanoparticles

A new thallium(I) coordination polymer, [Tl₂L · H₂O]_n ( 1 ) [H₂L = 5‐(4‐hydroxyphenyl)tetrazole], was synthesized and characterized by IR spectroscopy, elemental analysis, and X‐ray crystallography. The single‐crystal X‐ray diffraction data of compound 1 show the existence of two different Tl^I ions with differing coordination numbers. The coordination number of Tl^I(1) is four and that of Tl^I(2) is two. This coordination polymer was used as a precursor for the preparation of Tl^III oxide nanoparticles. Thallium(III) oxide was characterized by powder X‐ray diffraction and the morphology of nanoparticles characterized by scanning electron microscope (SEM).     

Synthesis and Crystal Structure of [Pb(phe)2]n: a 2D Coordination Polymer of Lead(II) Containing Phenylalanine

[Pb(phe)₂]_n ( 1 ) (phe is the abbreviation ofphenylalanine) have been synthesized and characterized by elemental analyses, IR and ¹H NMR spectroscopy. The single crystal structure of 1 show the complex to be a 2D chain polymer as a result of phenylalanine bridging. Coordination number of Pb^II ions is six, PbN₂O₄, with “stereo‐chemically active” electron lone pairs, and the coordination sphere is hemidirected. To the best of our knowledge, this 2D coordination polymer is the first amino acid lead(II) complex that characterized by X‐ray structural analysis.     

A Novel Polymeric Lead(II)‐Azido Compound: Synthesis,Structural Characterization,and DFT Calculations of [Pb(dmp)(N3)2]n

A novel 1D Pb^II coordination polymer containing Pb₂‐(μ‐N₃)₂ unit [Pb(dmp)(N₃)₂]_n (dmp =  2,9‐dimethyl‐1,10‐phenanthroline) has been prepared and characterized. Single‐crystal X‐ray diffraction analyses show that the coordination number for Pb^II ions is six, PbN₆, with “stereochemically active” electron lone pairs and the coordination sphere being hemidirected. The single‐crystal X‐ray data show the chains interact with each other through the π–π stacking interactions, which create a 3D framework. The structure of title complex has been optimized by density functional theory. Structural parameters and IR spectra for the complex are in agreement with the crystal structure.     

Different Coordination Modes of Saccharin in the Complexes of Lead(II) with 2‐Pyridylmethanol and Pyridine‐2, 6‐dimethanol — Synthesis,Spectral and Structural Characterization

New lead(II)‐saccharin complexes, [Pb(sac)₂(pym)] (1) and [Pb(sac)₂(pydm)] (2) (sac = saccharinate anion; pym = 2‐pyridylmethanol; pydm = pyridine‐2, 6‐dimethanol) were synthesized and characterized by IR spectroscopy and single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic P2₁/c space group with Z = 4, while the crystals of complex 2 are extremely X‐ray sensitive and decompose by the X‐ray beam within one day. Pym and pydm act as bi‐ and tridentate ligands, respectively. Most important feature of the complexes is non‐equivalent coordination of the sac ligands to the lead(II) atom. In the complex 1 , the sac ligands coordinate to the lead(II) ion in two distinct manners. One sac ligand behaves as a bridge between the lead(II) atoms through its N and carbonyl O atoms, whereas the other sac ligand acts as a bidentate chelating ligand through its N and carbonyl O atoms which is bicoordinating and also bridges the metal atoms to achieve the seven‐coordination. The structure is built up of three‐dimensional chains formed by the bridging of the PbN₃O₂ units and also held intermolecular hydrogen bonds. The IR spectra of the complexes were discussed in detail.     

A Novel Metal–Ligand Iodo‐bridged Lead(II) Compound: Synthesis,Crystal Structure,Thermal Properties,and DFT Calculations of [Pb(dmp)I2]n

. A novel 1D Pb^II coordination polymer [Pb(dmp)I₂]_n ( 1 ) (dmp = 2,9‐dimethyl‐1,10‐phenanthroline) containing a Pb₂‐(μ‐I)₂ unit was synthesized and characterized by elemental analysis, IR, ¹H NMR, and ¹³C NMR spectroscopy and studied by thermal analysis as well as X‐ray crystallography. The single‐crystal X‐ray data show that the coordination number of Pb^II ions is six, i.e. PbN₂I₄, with “stereo‐chemically active” electron lone pairs, and the coordination sphere is asymmetrical. They also show that the chains interact with each other through π‐π stacking interactions, which create a 3D framework. The structure of the title complex has been optimized by density functional theory calculations. The calculated structural parameters and the IR spectra of the title complex are in agreement with the crystal structure.     

Nonperipherally Octa(butyloxy)‐Substituted Phthalocyanine Derivatives with Good Crystallinity: Effects of Metal–Ligand Coordination on the Molecular Structure,Internal Structure,and Dimensions of Self‐Assembled Nanostructures

To investigate the effects of metal–ligand coordination on the molecular structure, internal structure, dimensions, and morphology of self‐assembled nanostructures, two nonperipherally octa(alkoxyl)‐substituted phthalocyanine compounds with good crystallinity, namely, metal‐free 1,4,8,11,15,18,22,25‐octa(butyloxy)phthalocyanine H₂Pc(α‐OC₄H₉)₈ ( 1 ) and its lead complex Pb[Pc(α‐OC₄H₉)₈] ( 2 ), were synthesized. Single‐crystal X‐ray diffraction analysis revealed the distorted molecular structure of metal‐free phthalocyanine with a saddle conformation. In the crystal of 2 , two monomeric molecules are linked by coordination of the Pb atom of one molecule with an aza‐nitrogen atom and its two neighboring oxygen atoms from the butyloxy substituents of another molecule, thereby forming a Pb‐connected pseudo‐double‐decker supramolecular structure with a domed conformation for the phthalocyanine ligand. The self‐assembling properties of 1 and 2 in the absence and presence of sodium ions were comparatively investigated by scanning electronic microscopy (SEM), spectroscopy, and X‐ray diffraction techniques. Intermolecular π–π interactions between metal‐free phthalocyanine molecules led to the formation of nanoribbons several micrometers in length and with an average width of approximately 100 nm, whereas the phthalocyaninato lead complex self‐assembles into nanostructures also with the ribbon morphology and micrometer length but with a different average width of approximately 150 nm depending on the π–π interactions between neighboring Pb‐connected pseudo‐double‐decker building blocks. This revealed the effect of the molecular structure (conformation) associated with metal–ligand (Pb? N_isoindole, Pb? N_aza, and Pb? O_butyloxy) coordination on the dimensions of the nanostructures. In the presence of Na⁺, additional metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds formed between sodium atoms and aza‐nitrogen atoms and the neighboring butyloxy oxygen atoms of two metal‐free phthalocyanine molecules cooperate with the intrinsic intermolecular π–π interactions, thereby resulting in an Na‐connected pseudo‐double‐decker building block with a twisted structure for the phthalocyanine ligand, which self‐assembles into twisted nanoribbons with an average width of approximately 50 nm depending on the intertetrapyrrole π–π interaction. This is evidenced by the X‐ray diffraction analysis results for the resulting aggregates. Twisted nanoribbons with an average width of approximately 100 nm were also formed from the lead coordination compound 2 in the presence of Na⁺ with a Pb‐connected pseudo‐double‐decker as the building block due to the formation of metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds between additionally introduced sodium ions and two phthalocyanine ligands of neighboring pseudo‐double‐decker building blocks.     

Three‐dimensional Hemidirected Mixed‐ligand Lead(II) Coordination Polymer, [Pb2(bpa)2(SCN)3(NO3)]n (bpa = 1,2‐di(4‐pyridyl)ethane)

A new 3D hemidirected mixed‐ligand lead(II) coordination polymer with the ligand 1,2‐di(4‐pyridyl)ethane bpa) and the two metal coordinated anions nitrate and thiocyanate, [Pb₂(bpa)₂(SCN)₃(NO₃)]_n ( 1 ), has been synthesized and characterized by CHN elemental analysis, IR‐, ¹H‐ and ¹³C NMR spectroscopy. The single crystal X‐ray data of compound 1 show that the complex is a three‐dimensional coordination polymer with two different Pb atoms with stereoactive electron lone pairs and six‐ and five‐coordinate hemidirected geometries, respectively.     

A Novel 1D Coordination Polymer [Pb(phen)(μ‐N3)(μ‐NO3)]n with the First Pb2‐(μ‐N3)2 Unit (phen = 1,10‐phenanthroline)

A novel 1D polymeric lead(II) complex containing the first Pb₂‐(μ‐N₃)₂ motif, [Pb(phen)(μ‐N₃)(μ‐NO₃)]_n (phen = 1,10‐phenanthroline), has been synthesized and characterized. The single‐crystal X‐ray data showed the coordination number of Pb²⁺ ions to be eight (PbN₄O₄) with the Pb²⁺ ions having “stereo‐chemically active” electron lone pairs; the coordination sphere is hemidirected. The chains interact with each other via π‐π interactions to create a 3D framework.     

两个含双(3,5－二甲吡唑基)甲烷配体的铅(II)配合物的合成与结构表征

Reactions of lead（Ⅱ） nitrate or perchlorate with bis（3,5-dimethylpyrazolyl）methane （dmpzm）, produced two new Pb（Ⅱ） chelated complexes [Pb（dmpzm）2X2] （X=NO3^- 1, ClO4^- 2）. Both compounds were structurally characterized by elemental analysis, IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. Both compounds are mononuclear with a distorted square antiprismatic PbN4O4 coordination geometry incorporating a pair of O,O＇-bidentate anions and N,N＇-bidentate dmpzm ligands. In the crystals of 1 or 2, the methyl or methylene groups of dmpzm ligand interact with the oxygen atoms of nitrates or perchlorates to afford intra- and intermolecular hydrogen bonding, thereby forming a two-dimensional network 1 or a three-dimensional structure 2.     

Synthesis and characterization of new coordination polymer with <Emphasis Type="SmallCaps">l</Emphasis>-proline amino acid ligand; new precursor for preparation of pure phase lead(II) oxide nanoparticles via thermal decomposition

A new two-dimensional lead(II) coordination polymer, [Pb(Pro)₂] _n (1); Pro = l-proline amino acid, has been synthesized and characterized by IR and X-ray diffraction. Structural determination of compound 1 reveals the Pb(II) ion is four-coordinated, bonded to two nitrogen atoms and two oxygen atoms from the l-proline ligand. PbO nanoparticles were synthesized by calcination of compound 1 at 500, 550 and 600 °C under air atmosphere. The PbO nanostructure was characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). The thermal stability of compound 1 was studied by thermal gravimetric analysis (TGA) and differential thermal analysis (DTA). Increase in calcination temperature decreased particles size and also led to layer-shape nanostructures morphology.     

Nano‐TiO2 as an Efficient Catalyst for Tandem Knoevenagel–Michael‐Cyclocondensation Reaction of Dimedone with Aromatic Aldehydes and Ammonium Acetate or Aromatic Amines under Solvent‐free Conditions

TiO₂ nanoparticles in anatase and rutile forms was characterized and studied by several techniques including X‐ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and successfully applied as an efficient and heterogeneous catalyst in the synthesis of 1,8‐dioxo‐decahydroacridines via the one‐pot multi‐component condensation reaction of dimedone with aromatic aldehydes and ammonium acetate or aromatic amines under mild and solvent‐free conditions.     

Hydrothermal Synthesis and Crystal Structure of a New Oxalato‐bridged Lead(II) Polymer: {[Pb(phen)2(ox)]·5H20}n (phen = 1, 10‐phenanthroline,ox = oxalate)

A new one‐dimensionally neutral coordination polymer, namely {[Pb(phen)₂(ox)]·5H₂0}_n (phen = 1, 10‐phenanthroline, ox = oxalate) ( 1 ), has been synthesized under hydrothermal condition and characterized by X‐ray crystallography. Complex 1 crystallizes in the orthorhombic space group Pban (No. 50) with a = 19.358(2), b = 6.8135(6), c = 9.7015(8)Å, V = 1279.6(2)ų, and Z = 2. Each Pb(II) atom is eight‐coordinated in a square‐antiprismatic D_4d geometry by four nitrogen atoms from two phen groups and four oxygen atoms from two ox ligands. The polymeric chains further constructed into a three‐dimensional network via strong π—π stacking interactions and hydrogen bonds. The complex exhibits intense blue photoluminescence with an emission maximum at 403 nm at room temperature.     

Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.     

Ultrasonic‐assisted synthesis of supramolecular copper (II) complex a precursor for the preparation of octahedron Cu2O nanoparticles applicable in the adsorption and photodegradation of Rhodamine B

A copper (II) supramolecular coordination complex formulated as [Cu₂(μ‐ox)₂(pyz)₃]_n ( 1 ), (pyz = pyrazine and ox = oxalate) has been synthesized under ultrasound irradiation. 1 was characterized using various techniques such as elemental analyses, Fourier‐transform infrared spectroscopy (FT‐IR), ultraviolet–visible spectroscopy (UV–Vis), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and single crystal X‐ray diffraction (SC‐XRD). A detailed magnetic characterization of complex 1 has been carried by vibrating sample magnetometer (VSM). The M‐H hysteresis loop of 1 revealed a weak ferromagnetic behavior with the highest magnetization of 0.0123 emu/g at room temperature. Compound 1 was used as an inorganic precursor to prepare Cu₂O nanoparticles through thermal decomposition at 600 °C. The obtained Cu₂O has been characterized using Fourier transform infrared spectroscopy (FT‐IR), X‐ray powder diffraction (XRPD) and scanning electron microscopy (SEM). The results of SEM showed octahedron Cu₂O nanoparticles with the edge lengths from 5–80 nm. Also, the adsorption ability and the photocatalytic activity of octahedral Cu₂O nanoparticles in the removal of rhodamine B (RB) have been investigated. The results showed that the obtained octahedral Cu₂O nanoparticles are effective in adsorption and degradation of rhodamine B from contaminated water sources. The maximum adsorption capacity and degradation efficiency of Cu₂O nanoparticles were 83.3 mg/g and 91.7%, respectively. It was also found that in comparison with the commercial Cu₂O, our fabricated Cu₂O nanoparticles exhibit higher catalytic activity.