Exploring C-F···π Interactions: Synthesis, Characterization, and Surface Analysis of Copper ß-Diketone Complexes.

Synthesis and characterization of two novel copper ß-diketone complexes, where halogen bonds play a pivotal role in shaping their multifaceted structural landscape, have been done in the present study. This study employs X-ray diffraction, ultraviolet-visible (UV-vis) spectroscopy, and infrared (IR) spectroscopy to investigate two copper ß-diketone complexes, [Cu(L1)2(ttfa)2]·2CH3OH (1) and [Cu(L1)(dfpb)2] (2), where Httfa is 4,4,4-trifluoro-1-(thiophen-2-yl)butan-3,1-dione and Hdfpb is 4,4-difluoro-1-phenylbutane-1,3-dione. Complex 1 displays a halogen bond, which contributes to its uniqueness. The coordination sphere around the copper atoms was found to be octahedral for complex 1 and pyramid with a square base for complex 2. The study also extensively discusses the interactions present in these complexes. Hirshfeld surface analysis was employed to gain a more detailed understanding of these interactions, and the results showed that hydrogen-bond interactions contributed above 30% of the whole surface area in both complexes. Additionally, the halogen bond in complex 1 was found to contribute approximately 8% of the surface. Overall, this study provides valuable insights into the structural properties and interactions of copper ß-diketone complexes, which could have potential applications in various fields.

MOFs as Versatile Catalysts: Synthesis Strategies and Applications in Value-Added Compound Production.

Catalysts played a crucial role in advancing modern human civilization, from ancient times to the industrial revolution. Due to high cost and limited availability of traditional catalysts, there is a need to develop cost-effective, high-activity, and nonprecious metal-based electrocatalysts. Metal-organic frameworks (MOFs) have emerged as an ideal candidate for heterogeneous catalysis due to their physicochemical properties, hybrid inorganic/organic structures, uncoordinated metal sites, and accessible organic sections. MOFs are high nanoporous crystalline materials that can be used as catalysts to facilitate polymerization reactions. Their chemical and structural diversity make them effective for various reactions compared to traditional catalysts. MOFs have been applied in gas storage and separation, ion-exchange, drug delivery, luminescence, sensing, nanofilters, water purification, and catalysis. The review focuses on MOF-enabled heterogeneous catalysis for value-added compound production, including alcohol oxidation, olefin oligomerization, and polymerization reactions. MOFs offer tunable porosity, high spatial density, and single-crystal XRD control over catalyst properties. In this review, MOFs were focused on reactions of CO2 fixation, CO2 reduction, and photoelectrochemical water splitting. Overall, MOFs have great potential as versatile catalysts for diverse applications in the future.

Lead(II)-Azido Metal-Organic Coordination Polymers: Synthesis, Structure and Application in PbO Nanomaterials Preparation.

The current study aims to explain recent developments in the synthesis of Pb(II)-azido metal-organic coordination polymers. Coordination polymers are defined as hybrid materials encompassing metal-ion-based, organic linkers, vertices, and ligands, serving to link the vertices to 1D, 2D, or 3D periodic configurations. The coordination polymers have many applications and potential properties in many research fields, primarily dependent on particular host-guest interactions. Metal coordination polymers (CPs) and complexes have fascinating structural topologies. Therefore, they have found numerous applications in different areas over the past two decades. Azido-bridged complexes are inorganic coordination ligands with higher fascination that have been the subject of intense research because of their coordination adaptability and magnetic diversity. Several sonochemical methods have been developed to synthesize nanostructures. Researchers have recently been interested in using ultrasound in organic chemistry synthetics, since ultrasonic waves in liquids accelerate chemical reactions in heterogeneous and homogeneous systems. The sonochemical synthesis of lead-azide coordination compounds resulted from very fantastic morphologies, and some of these compounds are used as precursors for preparing nano lead oxide. The ultrasonic sonochemistry approach has been extensively applied in different research fields, such as medical imaging, biological cell disruption, thermoplastic welding, food processing, and waste treatment. CPs serve as appropriate precursors for preparing favorable materials at the nanoscale. Using these polymers as precursors is beneficial for preparing inorganic nanomaterials such as metal oxides.

Ultrasonic-assisted synthesis and the structural characterization of novel the zig-zag Cd(II) metal-organic polymer and their nanostructures.

A sonochemical method was used to synthesize nano-rods of a novel cadmium(II) metal-organic coordination polymer, [Cd(p-2yeinh)(NO2)]n (1) (p-2yeinh = pyridin-2-yl ethylidene-isonicotinohydrazide). The effect of the synthesis parameters such as time, concentrations and irradiation power has been studied and optimized. It was shown that the thickness of rods has changed from 27 nm to 45 nm. The compounds were characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, X-ray powder diffraction (XPRD), and single crystal X-ray analysis. The X-ray structure analysis revealed that the Cd(II) atom is coordinated by one oxygen and three nitrogen atoms from two p-2yeinh ligands and two oxygen atoms of single nitrite anion with a CuN3O3 donor set with distorted octahedral geometry. The crystal taking the form of a one-dimensional zig-zag polymer. The adjacent chains connected by π-π of adjacent aromatic rings of p-2yeinh and other weak interactions. Consequently, the weak interactions also allow the 1D zig-zag structure to form a 3D metal-organic coordination polymer. CdO nanoparticles were prepared by thermolysis of compound 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XPRD to be 23 nm. The morphology and size of the prepared CdO nanoparticles were further studied using SEM.

Ultrasonic-assisted synthesis of nano lead(II) coordination polymer as precursors for preparation of lead(II) oxide nano-structures: Thermal, optical properties and XRD studies.

Nano structure of a lead (II) coordination polymer [Pb2(C2Cl3O2)2(NO3)2(Cl2H8N2)2]n (1), has been synthesized by a sonochemical method in different concentrations. The nano particles were characterized by scanning electron microscopy (SEM) X-ray powder diffraction (XRD), FT-IR spectroscopy and elemental analyses. The thermal stability of nano structure is closely investigated via thermal gravimetric (TGA), and compared with crystalline structure. The compounds are then heated to 600 °C to produce PbO nano particles. The resulting PbO is characterized through XRD and SEM analyses. Concentration of initial reagents effects on size and morphology of nano-structured compound 1 have been studied and show that low concentrations of initial reagents decreased particles size and leaded to uniform nano particles morphology. The photoluminescence properties of the prepared compound, as crystalline and as nanoparticles, have been investigated. The result showed a good correlation between the size and emission wavelength.

Thermolysis synthesis of pure phase NiO from novel sonochemical synthesized Ni(II) nano metal-organic supramolecular architecture.

Nano-structures of a new supramolecular coordination compound of divalent nickel with the pyrazol (pzH) containing the terminal azide anions, [Ni(pzH)2(N3)2] (1), with discrete molecular architecture (DMA) in solid state was synthesized via sonochemical method. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, IR, 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 Ni (II) ions is six, (NiN6), with four N-donor atoms from neutral "pzH" ligands and two N-donors from two terminal azide anions. The supramolecular features in these complexes are guided and controlled 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 consistent with the crystal structure. The NiO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant.

Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; New precursor for the preparation of nano-materials.

Nano-sheets of a novel Pb(II)-based 3D metal-organic coordination polymer [Pb2(nih)2(NO3)4(CH3OH)]n (1) were synthesized by a branched-tube method and sonochemical reaction. The synthesis was done using various times, concentrations of initial reagents, and irradiation power. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray powder diffraction (XRD), and single-crystal X-ray analysis. The X-ray analysis of the structures revealed the composition and stereochemistry of the basic building block, which had with a formula of {Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands and form infinite 3D metal-organic polymeric chains. The effect of triethylamine on the speed of nucleation was also investigated. Lead oxide nanoparticles were obtained by thermolysis of 1 at 180°C using oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XRD to be 36nm. The morphology and size of the PbO nanoparticles were also studied using SEM.

Sonochemical synthesis and structural determination of novel the nano-card house Cu(II) metal-organic coordination system.

A sonochemical method by using various time and concentrations of initial reagents and power of irradiation, was used to synthesize nano-card house of a new copper(II) metal-organic coordination system, {[Cu2(p-2yeinh)2Cl2]·(H2O)}n (1), where p-2yeinh=pyridin-2-yl ethylidene-isonicotinohydrazide. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, X-ray powder diffraction (XPRD), and single crystal X-ray analysis. The X-ray structure revealed that the Cu(II) atom is coordinated by one oxygen and three nitrogen atoms from two p-2yeinh ligands and one chloride anion with a CuN3OCl donor set with square pyramid geometry. This arrangement produces a large quadric nuclear square ring composed of four square pyramid Cu(II) moieties linked together by two p-2yeinh units (M4L4). The adjacent frameworks connected by strong hydrogen bonding interactions of methanol molecules that interact together and with the rings and π-π interactions of adjacent aromatic rings of p-2yeinh and other weak interactions. Consequently, the labile interactions also allow the discrete structure to form a 3D metal-organic coordination network. CuO 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 XPRD to be 38nm. The morphology and size of the prepared CuO nanoparticles were further studied using SEM.

Synthesis and characterization of nano-peanuts of lead(II) coordination polymer [Pb(qcnh)(NO3)2]n with ultrasonic assistance: A new precursor for the preparation of pure-phase nano-sized PbO.

A sonochemical method was used to synthesize nano-peanuts of a new lead(II) coordination 1D polymer, [Pb(qcnh)(NO3)2]n (1), where qcnh=2-quinolincarbaldehyde nicotinohydrazide. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), and single crystal X-ray analysis. The X-ray structure revealed that the Pb(II) atom is coordinated by one oxygen and three nitrogen atoms from two qcnh ligands and five oxygen atoms from three nitrate ligands in an 8+1 fashion with a PbN3O6 donor set. One of the PdN distances in the vicinity of the central atom is a bit longer (Pb1N1=2.939(4) Å), which shows the effect of the 6s2 lone electron pair localized within the valence shell of the lead(II) atom. 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 XRD to be 28nm. The morphology and size of the prepared PbO nanoparticles were further studied using SEM.

Ultrasound-assisted fabrication of a novel nickel(II)-bis-pyrazolyl borate two-nuclear discrete nano-structured coordination compound.

Ultrasound was used to synthesize nano-structures of [Ni(bpzB)2]2(1), a new two-nuclear discrete-coordination compound of divalent nickel with bis-pyrazolyl borate(bpzB). The nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, infrared, and elemental analysis. The single-crystal X-ray data show that the coordination number of Ni(II) ions is four (Ni1N4 and Ni2N4) with square planar geometry. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The discrete molecules interact with each other through labile interactions, creating a 3D supramolecular framework.

Ultrasound-assisted fabrication of a new nano-rods 3D copper(II)-organic coordination supramolecular compound.

High-energy ultrasound irradiation has been used for the synthesis of a new copper(II) coordination supramolecular compound, [Cu2(µ-O2CCH3)2(µ-OOCCH3)(phen)2](BF4) (1), ("phen" is 1,10-phenanthroline) with nano-rods morphology. The new nano-structure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction. The utilization of high intensity ultrasound has found as a facile, environmentally friendly, and versatile synthetic tool for the supramolecular coordination compounds.

Magnetic property, DFT calculation, and biological activity of bis[(µ(2)-chloro)chloro(1,10-phenanthroline)copper(II)] complex.

The dinuclear complex bis[(µ(2)-chloro)chloro(1,10-phenanthroline)copper(II)] (1) was synthesized, and characterized by X-ray, FTIR and thermal analysis. The fitting of magnetic susceptibility and magnetization curve of (1) indicates the occurrence of weak antiferromagnetic exchange interaction between copper(II) ions. The electronic structure has been also determined by density functional theory (DFT) method. Complex (1) displayed potent anticancer activity against B16 (Melanoma), MDA-MB-32 (Breast Adenocarcinoma), A549 (Lung Adenocarcinoma), HT-29 (Colon Adenocarcinoma) and SF (Astrocytoma) cell lines with an average IC50 value of 0.726 µg/ml compared to 4.88 µg/ml for cisplatin. Complex (1) has a better therapeutic index and toxicological profile than cisplatin, and has demonstrated a potential chemotherapeutic property.

Sonochemical syntheses of two new flower-like nano-scale high coordinated lead(II) supramolecular coordination polymers.

Two new neutral nano flower polymeric lead(II) coordination compounds, [Pb(tmph)(µ-SCN)2]n (1) and [Pb(tmph)(µ-NO3)2]n (2), [tmph=3,4,7,8-tetramethyl-1,10-phenanthroline], have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. SEM image shows the nano flower morphology for the products. Single-crystal X-ray studies show that the overall structure of the both 1 and 2 are 1D double chain net-like coordination polymers. Compound 1 has a very rare bridging cyanato pathway; a tetra dentate bridging between four Pb(II) centers. 1D double chains of compounds 1 and 2 further extended into two-dimensional (2D) and three dimensional (3D) supramolecular structures by strong π-π directional intermolecular interactions, respectively.

Sonochemical syntheses of binuclear lead(II)-azido supramolecule with ligand 3,4,7,8-tetramethyl-1,10-phenanthroline as precursor for preparation of lead(II) oxide nanoparticles.

The new neutral binuclear lead(II) azido coordination compound, [Pb 2(tmph) 2(µ-N3)2(CH3COO) 2] (1) [tmph = 3,4,7,8-tetramethyl-1,10-phenanthroline], has been synthesized by a sonochemical method. Single crystal X-ray structure shows that the overall structure of 1 is binuclear unit. Complex 1 has a bridging azido pathway, end-to-end bridging azides between a pair of lead(II) centers. This is further extended into a one-dimensional (1D) and three-dimensional (3D) supramolecular structure by Pb⋯C and π­π weak directional intermolecular interactions. The coordination number of lead(II) ions is seven, PbN4O3, with two N-donor atoms from tmph ligands and three O-donors from acetate 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 PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The morphology and size of the prepared PbO samples were further observed using scanning electron microscopy (SEM).

cis-Dioxido[N'-(2-oxidobenzyl-idene)pyridinium-4-carbohydrazidato-κO,N',O']vanadium(V).

The title Schiff base complex, [V(C(13)H(10)N(3)O(2))O(2)], features a square-pyramidal coordination geometry defined by the O,N',O'-donors of the tridentate Schiff base ligand and two oxide O atoms; one oxide O atom occupies the apical position. In the crystal, pyridinium-oxide N-H⋯O hydrogen bonds lead to zigzag supra-molecular chains with a flattened topology along [101]. The investigated crystal was twinned by nonmerohedry; the minor component refined to 18.5 (5)%.

catena-Poly[[(1,10-phenanthroline-κN,N')lead(II)]-di-µ-nitrato-κO,O':O'';κO:O',O''-[(1,10-phenanthroline-κN,N')lead(II)]-bis-(µ-2,2,2-trichloro-acetato-κO:O')].

In the title Pb(II) complex, [Pb(2)(C(2)Cl(3)O(2))(2)(NO(3))(2)(C(12)H(8)N(2))(2)](n), the 1,10-phenanthroline ligand is chelating, the nitrate anion chelates one Pb(II) ion and simultaneously bridges a neighbouring Pb(II) ion via the third O atom, and the trichloro-acetate anion is bidentate, bridging two Pb(II) ions. The coordination geometry is based on a penta-gonal-bipramidal geometry defined by an N(2)O(5) donor set with no obvious stereochemical role for the lead-bound lone pair of electrons. The coordination polymer has a zigzag topology along [010] and comprises alternating eight-membered {PbONO}(2) and {PbOCO}(2) rings.

Di-µ-chlorido-bis-[(1,10-phenanthroline-κN,N')(trichloro-acetato-κO)copper(II)].

The title compound, [Cu(2)(C(2)Cl(3)O(2))(2)Cl(2)(C(12)H(8)N(2))(2)], features a centrosymmetric binuclear complex. The coordination geometry around the Cu(II) atom is square-pyramidal, comprising two N atoms from a symmetrically chelating 1,10-phenanthroline ligand, one O atom from a trichloro-acetate ligand and two Cl(-) anions. In addition, there is a weak intra-molecular Cu⋯O inter-action of 2.9403 (14) Šinvolving the carbonyl O atom of the trichloro-acetate ligand. The central Cu(2)Cl(2) core takes the form of a rhombus, owing to the disparate Cu-Cl bond lengths. Mol-ecules are connected in the crystal structure by C-H⋯Cl and C-H⋯O inter-actions.

Dichlorido{1-[N-(5-chloro-2-oxidophen-yl)carboximido-yl]naphthalen-2-olato-κO,N,O'}(methanol-κO)tin(IV).

In the title complex, [Sn(C(17)H(10)ClNO(2))Cl(2)(CH(3)OH)], the Sn(IV) atom features a distorted octa-hedral geometry defined by the O,N,O'-donors of the dianion, two Cl atoms and the methanol O atom. The six-membered chelate ring has a half-chair conformation with the Sn atom lying 0.449 (4) Šout of the plane defined by the remaining atoms (r.m.s. deviation = 0.0238 Å). Supra-molecular helical chains along [100], mediated by O-H⋯O hydrogen bonds, feature in the crystal packing. Chains are linked by C-H⋯O, C-H⋯Cl and π-π [centroid-centroid distance = 3.598 (2) Å] inter-actions.

Bis{4-bromo-2-[(naphthalen-1-yl-imino)-meth-yl]phenolato-κN,O}copper(II).

The title complex, [Cu(C(17)H(11)BrNO)(2)], lies on a centre of inversion. The chelating Schiff base anions define a square-planar N(2)O(2) donor set. The nearly perpendicular orientation of the naphthyl residues of the chelate ring [dihedral angle = 82.12 (12)°] precludes the Cu(II) centre from additional coordination. In the refinement, the naphthyl rings were found to be disordered over two positions.; the major component has a site occupancy of 0.667 (4).

{4-Bromo-2-[(5-chloro-2-oxidophen-yl)imino-methyl]-phenolato-κO,N,O'}(methanol-κO)(methano-lato-κO)-oxidovanadium(V).

The title Schiff base complex, [V(C(13)H(7)BrClNO(2))(CH(3)O)O(CH(3)OH)], features a vanadyl group, a tridentate Schiff base ligand, and coordinated methanol and methano-late ligands. The NO(5) donor set is based on a distorted octa-hedron. Helical supra-molecular chains along [010] are found in the crystal structure mediated by O-H⋯O hydrogen bonds formed between the coordinating methanol mol-ecule and the phenolate O atom of the chloro-benzene residue.