The optical properties of 3 + 3 macrocyclic Schiff base thin material obtained by the Molecular Beam Epitaxy method.

3 + 3 optically active macrocyclic Schiff bases were synthesized in the reaction between 4-tert-butyl-2,6-diformylphenol with (1R,2R)-(+)-1,2-diphenylethylenediamine (S1) or (1S,2S)-(-)-1,2-diphenylethylenediamine (S1a). The new compounds were spectroscopically characterised by NMR, IR, X-ray (S1a), UV-Vis and fluorescence spectroscopy. The S1a molecule creates channels with distances between oxygen atoms ranging from 5.

Driving Forces in the Formation of Paracetamol Cocrystals and Solvate with Naphthalene, Quinoline and Acridine.

Paracetamol is an important analgesic and antipyretic drug showing poor tabletability. Among the various approaches used to improve this property, understanding the forces that govern the crystal packing is revealed to be crucial. We prepared three stable compounds: (par)∙(nap) (), (par)∙(quin) (), and (par)∙(acr) () (nap-naphthalene, quin-quinoline, acr-acridine) being cocrystals or solvate.

Exploring porosity in a flexible 3D organic-inorganic {ZnII3(4DPNDI)[W(CN)]} coordination network.

A 2D cyanido-bridged architecture Zn-[W(CN)] is smoothly pillared by ,'-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (4DPNDI) into 3D hybrid porous coordination polymer (PCP) {ZnII3(DMA)[W(CN)](4DPNDI)·8DMA}. It shows significant uptake of HO, MeOH or CHCl vapours with easy regeneration to the native form, and breathing-type CO adsorption contrasting non-porosity towards N, providing a new example of a highly flexible porous material.

Investigation of titanium(IV)-oxo complexes stabilized with α-hydroxy carboxylate ligands: structural analysis and DFT studies.

This paper explores the findings on the structures and physicochemical properties of titanium-oxo complexes (TOCs) stabilized by 9-hydroxy-9-fluorenecarboxylate ligands. Two complexes, with the overall formulas [TiO(OPr)(OCH)] (1) and [TiO(OPr)(OCH)(OCEt)] (2), have been synthesized. The structures of the isolated crystals (1 and 2) were determined using single-crystal X-ray diffraction.

Structural Characterization and Bioactivity of a Titanium(IV)-Oxo Complex Stabilized by Mandelate Ligands.

Research on titanium-oxo complexes (TOCs) is usually focused on their structure and photocatalytic properties. Findings from these investigations further sparked our interest in exploring their potential biological activities. In this study, we focused on the synthesis and structure of a compound with the general formula [TiO(OPr)(man)] (), which was isolated from the reaction mixture of titanium(IV) isopropoxide with mandelic acid (Hman) in a molar ratio of 4:1.

Nonlinear and Emissive {[M(CN)]···Polyresorcinol} (M = Fe, Co, Cr) Cocrystals Exhibiting an Ultralow Frequency Raman Response.

Optically active functional noncentrosymmetric architectures might be achieved through the combination of molecules with inscribed optical responses and species of dedicated tectonic character. Herein, we present the new series of noncentrosymmetric cocrystal salt solvates (PPh)[M(CN)](L)·solv (M = Cr(III), Fe(III), Co(III); L = polyresorcinol coformers, multiple hydrogen bond donors: 3,3',5,5'-tetrahydroxy-1,19-biphenyl, DiR, = 2, or 5'-(3,5-dihydroxyphenyl)-3,3″,5,5″-tetrahydroxy-1,19:3',1″-terphenyl, TriRB, = 1) denoted as and , respectively. The hydrogen-bonded subnetworks {[M(CN)];L} of , , or topology are formed through structural matching between building blocks within supramolecular -bis(chelate)-like {[M(CN)];(L)(L)} or tris(chelate)-like {[M(CN)];(L)} fragments.

Enantioselective Synthesis of Aza-Flavanones with an All-Carbon Quaternary Stereocenter via NHC-Catalyzed Intramolecular Annulation.

An enantioselective synthesis of functionalized -flavanone derivatives using the -heterocyclic carbene-catalyzed intramolecular Stetter reaction of sulphoamido benzaldehydes has been reported. This procedure presents the first original approach for synthesizing chiral functionalized flavonoids at the 3-position, containing an all-carbon quaternary stereogenic center. This advancement significantly enriches the chemical toolbox for the preparation of complex nitrogen-containing compounds and opens up new avenues for further research and development in synthetic organic chemistry.

Trityl-Based Lanthanide-Supramolecular Assemblies Exhibiting Slow Magnetic Relaxation.

The triphenylmethane (trityl) group has been recognized as a supramolecular synthon in crystal engineering, molecular machine rotors and stereochemical chirality inductors in materials science. Herein we demonstrate for the first time how it can be utilized in the domain of molecular magnetic materials through shaping of single molecule magnet (SMM) properties within the lanthanide complexes in tandem with other non-covalent interactions. Trityl-appended mono- (HL ) and bis-compartmental (HL ) hydrazone ligands were synthesized and complexated with Dy(III) and Er(III) triflate and nitrate salts to generate four monometallic (1-4) and two bimetallic (5, 6) complexes.

Difluoroborate-based bichromophores: Symmetry relaxation and two-photon absorption.

Given potential applications of multiphoton absorbers, in the present work we have studied the symmetry-relaxation effects in one- and two-photon absorption spectra in two bichromophore systems based on difluoroborate core linked by biphenylene or bianthracene moieties. We have employed a palette of experimental methods (synthesis, one- and two-photon spectroscopy, X-ray crystallography) and state-of-the-art computational methods to shed light on how symmetry relaxation, a result of twisting of building blocks, affects one- and two-photon absorption of the two studied fluorescent dyes. Electronic-structure calculations revealed that the planarity of central biphenyl moiety, as well as deviations from planarity up to 30-40 deg.

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples.

The procedures of putrescine, spermine, spermidine, and cadaverine derivatization using 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene, 1-fluoro-2-nitro-4-(trifluoromethyl) benzene, and 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for chromatographic determination in home-made wine samples are compared in the present study. The procedures discussed were compared regarding simplicity, linearity, precision, and accuracy. The polyamines derivatives were isolated and characterized by X-ray crystallography and H, C, and F NMR spectroscopy.

New Dinuclear Macrocyclic Copper(II) Complexes as Potentially Fluorescent and Magnetic Materials.

Two dinuclear copper(II) complexes with macrocyclic Schiff bases and were prepared by the template reaction of ()-(+)-1,1'-binaphthalene-2,2'-diamine and 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde , or 4--butyl-2,6-diformylphenol with copper(II) chloride dihydrate. The compounds were characterized by spectroscopic methods. X-ray crystal structure determination and DFT calculations confirmed their geometry in solution and in the solid phase.

Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)] Unit.

The new heterometallic compounds, [{Cu(pn)}Ni(NCS)]·2nHO (), [{Cu(trien)}Ni(NCS)Cu(NCS)] () and [Cu(tren)(NCS)][Ni(NCS)] () (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds , and show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.

Luminescence and Dielectric Switchable Properties of a 1D (1,1,1-Trimethylhydrazinium)PbI Hybrid Perovskitoid.

The synthesis and investigation of the physicochemical properties of a novel one-dimensional (1D) hybrid organic-inorganic perovskitoid templated by the 1,1,1-trimethylhydrazinium (MeHy) cation are reported. (MeHy)[PbI] crystallizes in the hexagonal 6/ symmetry and undergoes two phase transitions (PTs) during heating (cooling) at 322 (320) and 207 (202) K. X-ray diffraction data and temperature-dependent vibrational studies show that the second-order PT to the high-temperature hexagonal 6/ phase is associated with a weak change in entropy and is related to weak structural changes and different confinement of cations in the available space.

Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine.

Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde , respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of and were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots.

Supramolecular -"Bis(Chelation)" of [M(CN)] (M = Cr, Fe, Co) by Phloroglucinol (HPG).

Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic -metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh)[M(CN)](HPG)·2MeCN (M = Cr, ; Fe, ; Co ; HPG = phloroglucinol, 1,3,5-trihydroxobenzene).

Titanium(IV) Oxo-Complex with Acetylsalicylic Acid Ligand and Its Polymer Composites: Synthesis, Structure, Spectroscopic Characterization, and Photocatalytic Activity.

The titanium oxo complexes are widely studied, due to their potential applications in photocatalytic processes, environmental protection, and also in the biomedical field. The presented results concern the oxo complex synthesized in the reaction of titanium(IV) isobutoxide and acetylsalicylic acid (Hasp), in a 4:1 molar ratio. The structure of isolated crystals was solved using the single-crystal X-ray diffraction method.

New dinuclear zinc(ii) complexes with Schiff bases obtained from -phenylenediamine and their application as fluorescent materials in spin coating deposition.

Two Zn(ii) complexes, K1 and K2, obtained from the template reaction of zinc(ii) acetate dihydrate with -phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde (K1) or 2-hydroxy-5--butyl-1,3-benzenedicarboxaldehyde (K2), respectively, were characterized by X-ray crystallography, spectroscopic (UV-vis, fluorescence and IR), and thermal methods. In the complex [Zn(MeO)(OH)(L1)]·2HO K1, there are two binding sites in the macrocyclic ligand and they are occupied by zinc(ii) cations found in slightly distorted square pyramidal environment. The zinc(ii) cations are connected by slightly asymmetric oxo bridges with a Zn1-O14-Zn1[-, - + 1, - + 1] angle of 104.

Sorption and Magnetic Properties of Oxalato-Based Trimetallic Open Framework Stabilized by Charge-Assisted Hydrogen Bonds.

We report a new structure of {[Co(bpy)(ox)][{Cu(bpy)(ox)}Fe(ox)]}·8.5nHO presenting a rare ladder topology among oxalate-based coordination polymers with anionic chains composed of alternately arranged [Cu(bpy)(ox)] and [Fe(ox)] moieties. Along the a axis, they are separated by Co(III) units to give porous material with voids of 963.

NHC-catalyzed enantioselective C2-functionalization of 3-hydroxychromenones α,β-unsaturated acyl azoliums.

A novel synthetic method for enantioselective C2-functionalization of 3-hydroxychromenones promoted by N-heterocyclic carbenes the formation of α,β-unsaturated acyl azolium intermediates, which occurs with Coates-Claisen rearrangement is established. This synthetic strategy enabled the rapid assembly of enantiomerically enriched δ-hydroxychromenone-derived esters/amides under mild conditions with good to excellent yields and broad substrate scope.

Dinuclear Copper(II) Complexes with Schiff Bases Derived from 2-Hydroxy-5-Methylisophthalaldehyde and Histamine or 2-(2-Aminoethyl)pyridine and Their Application as Magnetic and Fluorescent Materials in Thin Film Deposition.

Two Cu(II) complexes, and , with tridentate Schiff bases derived from 2-hydroxy-5-methylisophthalaldehyde and histamine or 2-(2-aminoethyl)pyridine , respectively, were obtained and characterized by X-ray crystallography, spectroscopic (UV-vis, fluorescence, IR, and EPR), magnetic, and thermal methods. Despite the fact that the chelate formed by the NNO ligand donors (C26-C25H-C24H-N23=C23H-C22-C19Ph(O1)-C2(Ph)-C3H=N3-C4H-C5H-C6 fragment) are identical, as well as the synthesis of Cu(II) complexes (Cu:L = 2:1 molar ratio) was performed in the same manner, the structures of the complexes differ significantly. The complex , {[Cu(L1)Cl][CuCl]}·2MeCN·2HO, consists of [Cu(L1)Cl] units in which Cu(II) ions are bridged by the ligand oxygen and each of these Cu(II) ions is connected with Cu(II) ions of the next dimeric unit via two bridging Cl ions to form a chain structure.

Trinuclear Oxo-Titanium Clusters: Synthesis, Structure, and Photocatalytic Activity.

The interest in titanium (IV) oxo-complexes is due to their potential application in photodegradation processes and environmental pollutants reduction. Titanium (IV) oxo-complexes (TOCs) of the general formula [TiO(OPr)(OOCR')] (R' = -CH (), --PhCl (), PhNO (), -CH ()) were synthesized and structurally characterized. The use of the different carboxylate ligands allowed modulating the optical band gaps of the produced microcrystals, which were measured via diffuse reflectance ultraviolet and visible spectroscopy (UV-Vis-DRS) and calculated using the density functional theory (DFT) method.

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate(iii) unit with the green → blue → red crystal color sequence.

Three new complexes forming a dynamic system and given by the following formulae: [Cu(bpy)Fe(ox)]NO·HO 1, [Fe(bpy)][Fe(ox)]NO·10HO 2 and [Cu(bpy)][Fe(ox)]NO·10HO 3 (bpy - 2,2'-bipyridine, ox - oxalate), were synthesized from a methanol-water mixture or water, and characterized structurally, spectroscopically and magnetically. Compound 1 contains trinuclear [(bpy)Cu(μ-ox)Fe(ox)(μ-ox)Cu(bpy)] cations, while 2 and 3 can be classified as isomorphous ionic compounds, with alternately arranged hydrophobic and hydrophilic layers of mononuclear complex ions. The green crystals of 1 are perfectly stable in air, whereas in selected solvents they undergo irreversible solvent-assisted recrystallization towards red crystals of 2, which is also accompanied by the appearance of mononuclear blue copper complexes with oxalate, 2,2'-bipyridine and aqua ligands, already described in the literature.

Synthesis, X-ray structure, physicochemical properties and anticancer activity of mer and fac Ru(iii) triphenylphosphine complexes with a benzothiazole derivative as a co-ligand.

Two mononuclear ruthenium(iii) mer- and fac-isomers of the formula [RuCl3(PPh3)(dmpbt)] (where PPh3 = triphenylphosphine, dmpbt = 2-(3,5-dimethylpyrazoll-yl)benzothiazole) have been synthesised from the reaction of [RuCl3(PPh3)3] with a bidentate ligand - dmpbt. Appropriate reaction conditions allowed obtaining the two isomers separately without separation techniques. X-ray crystallography has determined the crystal and molecular structures of the new complexes.

Studies on Silver Ions Releasing Processes and Mechanical Properties of Surface-Modified Titanium Alloy Implants.

Dispersed silver nanoparticles (AgNPs) on the surface of titanium alloy (Ti6Al4V) and titanium alloy modified by titania nanotube layer (Ti6Al4V/TNT) substrates were produced by the chemical vapor deposition method (CVD) using a novel precursor of the formula [Ag₅(O₂CC₂F₅)₅(H₂O)₃]. The structure and volatile properties of this compound were determined using single crystal X-ray diffractometry, variable temperature IR spectrophotometry (VT IR), and electron inducted mass spectrometry (EI MS). The morphology and the structure of the produced Ti6Al4V/AgNPs and Ti6Al4V/TNT/AgNPs composites were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM).