DFT(B3LYP/LanL2DZ), non-linear optical and electrical studies of a new hybrid compound: [C6H10(NH3)2]CoCl4·H2O

A new organic-inorganic material [C₆H₁₀(NH₃)₂]CoCl₄·H₂O was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, thermal analysis and dielectric technique. It crystallizes in the non-centrosymmetric space group Pna2₁ with the following unit cell parameters: a=12.5328(1) Å, b=9.0908(1) Å, c=11.7440(1) and α=β=γ=90°. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated H₂O, isolated [CoCl₄]²⁻ tetrahedral anions and diammoniumcyclohexane [C₆H₁₀(NH₃)₂]²⁺ cations, which are connected via N–H…Cl, N–H…O and O–H…N hydrogen bonds. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. Theoretical calculations were performed using DFT/B3LYP/LanL2DZ method for studying the molecular structure and vibrational spectra and especially to examine the non-linear optical behavior of the compound. Solid state ¹³C NMR spectrum shows three signals correspond to three different carbon environments. Thermal analysis discloses a phase transition at the temperature 315 K and the evaporation of water molecule at 327 K. A detailed dielectric study was reported and shows a good agreement with thermal measurements.     

A promising guanidinium based metal-organic single crystal for optical power limiting applications

A novel guanidinium based metal-organic framework material [(2(C H₆ N₃)⁺.Zn (C₂H₃O₂)₄]− has been synthesized and optical transparency of the crystals was studied. Structural parameters of the grown metal-organic crystals have been characterized by single crystal X-ray diffraction. The single crystal XRD study confirms that the title compound crystallized in tetragonal system with I 4₁ /a c d space group. The crystal structure has stabilized through intricate 3-D hydrogen bonding network established by the NH…O and CH…O interactions. The soft nature of the material has been identified by hardness study. UV–visible spectroscopy has been used to investigate the optical properties. Good thermal stability has been proved by TG-DTA. The third order nonlinear optical response was studied by Z-Scan technique.     

Crystal structure,Hirshfeld surface analysis,vibrational properties,and electrical and dielectric studies of the bis (4-benzylpyridinium) tetrachlorocuprate (II)

The present paper undertakes the study of (C₁₂H₁₂N)₂CuCl₄, which is a new hybrid compound. It is synthesized and characterized by single-crystal X-ray diffraction, Hirshfeld surface analysis, and FT-IR, FT-Raman, and impedance spectroscopies. It is crystallized in the monoclinic system with C2/c space group. Its crystal structure was determined and refined down to an R value of 0.05 and a wR value of 0.14. The structure can be described by the alternation of two different, cationic–anionic layers parallel to (110) plan. This complex is assembled into 3D supramolecular architecture by hydrogen bonds (N–H…Cl, C–H…Cl) and π–π interactions. Hirshfeld surface analyses and fingerprint plots are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The presence of different functional groups and the nature of their vibrations were identified by FT-IR and FT-Raman spectroscopies. The material is characterized by impedance spectroscopy technique measured in 209–500 MHz frequency and 296–390 K temperature ranges. In addition, the Cole–Cole (Z? versus Z?) plots were well fitted to an equivalent circuit built up by a parallel combination of resistance (R) and constant phase elements (CPEs). The close values of activation energies obtained from the analysis of equivalent circuit data confirm that the transport is through ion hopping mechanism in the bis (4-benzylpyridinium) tetrachlorocuprate.     

Synthesis,crystal growth,and characterization of piperazinediium bis (4-aminobenzoate) dihydrate - An efficient third-order nonlinear optical single crystal for opto-electronic applications

Organic compound of protonated Piperazinediium bis (4-aminobenzoate) dihydrate C₄H₁₂N₂²⁺2(C₇H₆NO₂⁻).2(H₂O) (PZ4AB) was synthesized and crystal was grown by slow evaporation solution growth technique. Powder X-ray diffraction and High resolution X-ray diffraction studies affirmed the crystalline perfection of the grown crystal. Fourier transform infrared spectral analysis ascertained the frequencies of various functional groups present in PZ4AB crystal. Optical transmittance and optical band gap estimation explored the optical phenomena of PZ4AB crystal. The laser-induced surface damage threshold value of PZ4AB crystal was measured to be 1.0615 GW/cm² for the 1064 nm Nd:YAG laser radiation. From Thermogravimetric and differential scanning calorimetric studies, the stability of PZ4AB crystal was ascertained. The dielectric manner was endowed as a function of frequency and temperature. The mechanically soft nature of the crystal was assessed by Vickers hardness measurement which exhibited the reverse indentation size effect. The nonlinear refractive index, absorption coefficient and the third-order nonlinear susceptibility of crystal were divulged by Z-scan technique.     

Synthesis,structural characterization,spectroscopic, thermal,dielectric and Hirshfeld surface analysis of 1-(2-methoxyphenyl)piperazinium chloranilate

The new compound 1-(2-methoxyphenyl)piperazinium chloranilate (MPP.CA) was synthesized and studied by the single crystal X-ray diffraction method. Its structure was confirmed by infrared spectroscopy. The crystal structure consists of ribbons of chloranilate anions and 1-(2-methoxyphenyl)piperazinium cations linked together by NH…O hydrogen bonds. Two protons are transferred from a chloranilic acid molecule to the nitrogen of the piperazine in this structure. Measurements of AC conductivity as a function of frequency at different temperatures indicated the hopping conduction mechanism; in addition, the variation of dielectric constant as a function of T confirmed the transition phase indicated by the differential scanning calorimetry (DSC). The physico-chemical properties, UV-Vis, DSC and dielectric properties are described. Hirshfeld surface analyzes all the intermolecular interactions involved within the structure, which are important to stabilize the structure.     

Optical, thermal, dielectric and ferroelectric behaviour of sodium acid phthalate (SAP) single crystals

Sodium acid phthalate (SAP), an efficient semi-organic crystal having dimensions 17×8×2 mm³ has been grown from aqueous solution by slow evaporation technique at room temperature within the period of 2 weeks. The lattice parameters of the grown crystals were determined using single-crystal X-ray diffraction analysis. The presence of functional groups was estimated qualitatively by Fourier transform infrared (FTIR) analysis. The band gap energy was determined using optical absorption studies. The TG/DTA analysis reveals that the SAP crystal is thermally stable up to 141.6 °C. The dielectric constant and dielectric loss was studied as a function of frequency and the corresponding activation energy (E_a) has been calculated for the grown crystal. Scanning electron microscope studies enunciate the ferroelectric domain patterns of the SAP crystal. Ferroelectric property of the grown crystal was confirmed by hysteresis loop studies.     

Synthesis,optical, dielectric,thermal and mechanical properties of a nonlinear optical amino acid crystal: Bis-glycine hydrobromide

A semi organic material Bis-glycine hydrobromide (C₄H₁₁N₂O₄⁺Br⁻) has been synthesized by slow solvent evaporation technique. The grown crystal was subjected to single crystal X-ray diffraction studies and its crystal parameters were confirmed. The FTIR analysis confirms the presence of various functional groups present in the title compound. The Kurtz powder second harmonic generation test shows that the crystal is a potential candidate for optical second harmonic generation. The UV–vis spectrum reveals the transparency of the crystal and enumerates the direct band gap energy of the material. The dielectric constant and the dielectric loss were studied as a function of frequency. The thermal studies indicate that the material is thermally stable up to 290 °C. The hardness number was calculated to be 110 kg/mm² from the Vicker's microhardness test.     

Growth,spectral, optical,and dielectric studies on novel semiorganic NLO single crystal: d-phenylglycine hydrochloride

Good quality novel semiorganic nonlinear optical single crystal of d-phenylglycine hydrochloride has been grown from the aqueous solution by low temperature solution growth method. X-ray diffraction reveals that the crystal crystallises into orthorhombic system with noncentrosymmetric space group P2₁2₁2₁. Experimental parameters are evaluated based on single-crystal XRD and the calculated values of the polarisability were compared with the values of polarisability using Clausius–Mossotti equation. The functional groups present in the grown crystal were confirmed by Fourier transform infrared spectral analysis. The ¹H and ¹³C FT–NMR has been recorded to elucidate the molecular structure. Ultraviolet–visible-near infra-red absorption studies on this crystal reveal that the minimum absorption region is around 228 nm. The optical band gap of the crystal was found to be 2.9 eV. The scanning electron microscope study has been carried out to determine the surface morphology of the grown crystal. Photoluminescence studies show that the material emits violet fluorescence. Thermal studies bring forth that the crystal is thermally stable up to 255 °C. Dielectric studies reveal that both the dielectric constant and dielectric loss decrease with the increase in frequency as like the typical semiorganic nonlinear optical crystals such as bisthiourea zinc chloride, bisthiourea cadmium chloride and l-arginine dihydrogen phosphate. Electrical conductivity measurements were carried out and the Arrhenius plot is used to determine the value of activation energy. The Kurtz powder analysis on the crystal confirms the existence of second harmonic generation properties. The SHG efficiency was found to be 1.15 times that of KDP crystal.     

Synthesis,crystal structure,Hirshfeld surface analysis,and vibrational and DFT investigation of [C<Subscript>6</Subscript>H<Subscript>10</Subscript>(NH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>CuBr<Subscript>4</Subscript>.3Br

Single crystal of a new organic–inorganic hybrid material [C₆H₁₀(NH₃)₂]₃CuBr₄.3Br was synthesized by the slow evaporation method at room temperature and characterized by X-ray diffraction, FTIR, Raman spectroscopy, UV–Vis, dielectric measurements, and Hirschfield surface analysis. The title compound crystallizes in trigonal system \( P\overline{3} \).The crystal packing is governed by the N-H…Br and non-classical C-H…Br hydrogen-bonding interactions between the 1, 2-diamoniumcyclohexane cations, the tetrahedral [CuBr₄]^3? anions, and the isolated ion Br^?. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra, and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The optical properties were investigated by optical absorption and show two bands at 260 and 305 nm.     

Structural study,intermolecular interactions in view of X-ray and Hirshfeld surface analysis,DSC characterization,and electrical properties of <Emphasis Type="Italic">bis</Emphasis>-(4-benzylpyridinium) tetrabromozincate

The synthesis and crystal structure of the bis-(4-benzylpyridinium) tetrabromozincate(II) “(4-BP)₂[ZnBr₄]” salt are reported in the present paper. After an X-ray investigation, it has been shown that the title compound belongs to the centrosymmetric monoclinic system at 296 K, in the space group P2₁/n with the following lattice parameters a = 15.0764(8) Å, b = 22.5575(12) Å, c = 16.0739(9) Å, and β = 93.887(3)°. The FT-IR and Raman spectra confirm the presence of both cationic and anionic parts. The crystal packing is governed by an extensive network: N–H…Br, (N: pyridinium), C–H…Br hydrogen bonds, π…π, and C–H…π stacking between identical 4-BP (aromatic–aromatic), in which they may be effective in the stabilization of the crystal structure. Moreover, Hirshfeld surface analysis was used for visually analyzing intermolecular interactions in crystal structures. The phase transitions at T = 323 K have been confirmed by the differential scanning calorimetry. The electrical technique was measured in the 209 Hz–5-MHz frequency range and 298–393-K temperature intervals. The evolution of the dielectric constant as a function of frequency and temperature proved the presence of a first-order phase transition at 323 K.

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Graphical abstract ?

     

Growth, microhardness, dielectric and photoconductivity characterization of a highly polarizable NLO material: Sodium p-nitrophenolate dihydrate (NO2-C6H4-ONa.2H2O)

Sodium p-nitrophenolate dihydrate (NPNa.2H₂O) is a highly polarisable non linear optical material. It has a d_eff about 1.45 times than that of potassium titanyl phosphate. Single crystals of (NPNa.2H₂O) have been grown successfully by slow solvent evaporation having water and methanol as solvent. The structure of the crystal is verified by single X-ray analysis. Optical absorption shows that the crystal is highly transparent between 1500 and 300 nm. Microhardness of the crystal is found to increases with increase in load and the hardness number is found to be high for methanol grown crystal as compared to the water grown crystal. Electrical conductivity as evaluated from the cole-cole plot is found to be 1.26 × 10⁻⁵ mho m⁻¹. The dielectric constant of the crystal is low and independent at higher frequencies. The crystal has prominent photoconduction in the presence of trap energy levels formed by the Na⁺ ions. The SHG efficiency of the crystal is studied by performing Kurtz powder test and the results of scanning electron microscope analysis indicate that the major part of the crystal surface is free from inclusion and dislocation.     

Metal-ion binding via a cyclic network of intramolecular halogen-bonded interactions: a theoretical study

A cyclic network of four intramolecular C–I…N interactions is shown to bind Na⁺ and Ca²⁺ with corresponding binding energies of 57 and 175 kcal/mol, respectively. The halogen-bonded network is built by connecting four molecules of 2-iodoimidazole with acetylene and ethylene as convenient linkers. 2-iodoimidazole provides both the halogen bond donor and the halogen bond acceptor moieties. Each of the four iodine atoms participates in the binding of the metal ion as indicated by the presence of bond paths connecting the metal ion with each one of the halogen atoms in the host, and orthogonal to the C–I…N interactions. A similar intermolecular network of C–I…N interactions is also found to form by the interactions of four 2-iodoimidazole molecules. In contrast to its intramolecular counterpart, the intermolecular C–I…N network is at least partly destroyed upon metal-ion binding as the metal ion competes somewhat successfully for the lone pair of the acceptor nitrogen atoms.     

Two salts and the salt cocrystal of ciprofloxacin with thiobarbituric and barbituric acids: The structure and properties

Ciprofloxacin (CfH, C₁₇H₁₈FN₃O₃) crystallizes with 2‐thiobarbituric (H₂tba) and barbituric acid (H₂ba) in the aqueous solution to yield salt CfH₂(Htba)·3H₂O ( 1 ), salt cocrystal CfH₂(Hba)(H₂ba)·3H₂O ( 2 ), and salt CfH₂(Hba)·H₂O ( 3 ). The compounds are structurally characterized by the X‐ray single‐crystal diffraction. The numerous intermolecular hydrogen bonds N–H?O and O–H?O formed by water molecules, Htba^?/Hba^? and CfH₂⁺ ions, and H₂ba molecules stabilize the crystal structures of 1 to 3 . Hydrogen bonds form a 2D plane network in the salts of 1 and 3 and a 3D network in the salt cocrystal of 2 . There are different π‐π interactions in 1 to 3 . The compounds have been characterized by powder X‐ray diffraction, thermogravimetry/differential scanning calorimetry, and Fourier transform infrared spectroscopy. The compounds dehydration ends at 130°C to 150°C, and their oxidative decomposition is observed in the range of 250°C to 275°C.     

Synthesis, crystal structure, spectral and thermal properties of 4-dimethylaminopyridinium salicylate monohydrate

4-dimethylaminopyridinium salicylate monohydrate (DMAPSA) was synthesized and its crystal structure was determined using single crystal X-ray diffraction analysis. From the crystal structure analysis it can be inferred that the crystal belongs to monoclinic system with space group of P2₁/n. Investigation has been carried out to assign the vibrational frequencies of the grown crystals by FTIR spectral studies. ¹H and ¹³C FT–NMR has been recorded to elucidate the molecular structure. The molecular mass of DMAPSA has been measured using mass spectroscopic analysis. The thermal stability and thermal decomposition of DMAPSA have been investigated by means of thermogravimetric analysis and differential thermal analysis. The melting point of crystal was observed as 172 °C by melting point apparatus. Fluorescence spectra were taken for the excitation wavelength of 240 nm.     

Ultrasound-assisted synthesis of two novel [CuBr(diamine)2·H2O]Br complexes: Solvatochromism,crystal structure,physicochemical, Hirshfeld surface thermal,DNA/binding,antitumor and antibacterial activities

Two new hydrated monocationic Cu(II) complexes with 1,3-propylenediamine and 1,2-ethylenediamine of general formula [CuBr(N-N)₂·H₂O]Br were prepared. The complexes were identified by means of several spectroscopic tools (Uv-visible, IR and MS), thermally (TG/DTA) and CHN-elemental analysis. The three dimensional structure for complex A and B was provide by X-ray diffraction studies and showed the Cu(II) ion as 4 + 1 + 1 coordinated, four nitrogen atoms of the diamine ligands, one bromide ion and one H₂O semi-coordinated to the Cu(II) center, a typical trans effect is clearly observed in the two complexes. The molecular crystal structures are linked via several H-bonds like N_H…Br and N_H…O. Additionally, intra-molecular H-bonds of kind C_H…Br is observed; these interactions lead to crystal structure three dimensional architecture packing. Hirshfeld surfaces (HSA) analysis was served to figure out the inter-contacts and fingerprints atoms percentage. DNA-binding, antitumor and antibacterial effectiveness of the desired complexes were evaluated.     

Ions with strong symmetric H-bonds and their solvation in aqueous-ethanolic solutions of HCl

Ion-molecular interactions in the HCl-EtOH-H₂O system are studied by means of multiple frustrated total internal reflection IR spectroscopy over a wide range of concentrations of the components. It is demonstrated that, in the investigated solutions, the acid is fully bound into ions and uncharged complexes formed by strong symmetric or quasi-symmetric H-bonds. There is a competition between H₂O and EtOH molecules during the formation of the (H₅C₂(H)O…H…O(H)C₂H₅)⁺, (H₂O…H…OH₂)⁺, and (H₂O…H…O(H)C₂H₅)⁺ proton disolvates. In dilute solutions of HCl in 2: 1 and 1: 1 EtOH-H₂O mixtures, (H₂O…H…OH₂)⁺ proton dihydrates are mainly formed, whereas in concentrated HCl solutions, under conditions of a partial solvation of ions by solvent molecules, predominantly (H₂O…H…O(H)C₂H₅)⁺ mixed proton disolvates arise. In concentrated solutions of HCl in EtOH with low water content, the acid is partially bound into (H₅C₂(H)O…H⁺…Cl^?) uncharged complexes with the participation of the Cl^? anion.     

单甲基化及双乙基化大豆苷元磺酸锰的合成及晶体结构

以大豆苷元为先导化合物,合成了两种水溶性异黄酮磺酸锰：7-甲氧基-4′-羟基异黄酮-3′-磺酸锰（1）和4′,7-二乙氧基异黄酮-3′-磺酸锰（2）,并采用1HNMR、IR光谱、元素分析和X-射线单晶衍射法对它们的结构进行了表征。X-射线单晶衍射分析表明：1的分子组成为[Mn（H2O）6]（C16H11O4SO3）2.10H2O,其中Mn（II）位于对称中心并被6分子水所配位。[Mn（H2O）6]^2＋,C16H11O4SO3-和H2O之间存在多种氢键;2的分子组成为[Mn（H2O）6]（C19H17O4SO3）2.8H2O,两个异黄酮骨架构象不同。6个配位水分子分别与2个异黄酮骨架中磺酸根上的4个氧原子及8个结晶水上的8个氧原子形成12条氢键。1,2的晶体结构中均存在着π…π堆积作用,氢键以及π…π堆积作用共同将1或2组装成具有三维网格结构的超分子。     

Investigation on inorganic potassium lithium sulfate single crystal grown by SR method and its characterization for nonlinear optical application

Inorganic crystal lithium potassium sulfate (LKS) was grown by Sangaranarayanan-Ramasamy technique. Structural parameters of the grown LKS crystal were confirmed by single crystal X-ray diffraction analysis. LKS crystal belongs to hexagonal system with non-centrosymmetric space group P6₃. The functional elements presented in the compound were analyzed by ICP-OES test. Thermal property of the sample was evaluated by tracing TGA and DSC plots. UV–Vis spectral studies revealed the lower cut-off wavelength, transparency and band gap (4.9 eV) of LKS crystal. Multi-shot laser damage threshold value of LKS crystal was found to be 4.2 GW/cm². Using Kurtz and Perry powder technique, the second harmonic generation (SHG) efficiency was found. The photoluminescence, dielectric, mechanical and etching studies were also studied to test the LKS crystal for NLO application.     

A computational study of model hydrogen-, halogen-, beryllium- and magnesium-bonded complexes of aziridine derivatives

ABSTRACT

A computational study of the complexes F^?/H₂O…Z-aziridine, Z-aziridine…BeH₂/MgH₂ and F^?/H₂O…Z-aziridine…BeH₂ /MgH₂ (Z = Cl, H, Li) was undertaken in order to investigate the non-covalent interactions operative in the dimers and to assess their interplay in the trimer complexes. The halogen- and hydrogen-bonds between the O and Z atoms in F^?/H₂O…Z-aziridine are enhanced in the trimers by the Be(Mg) bond and vice versa, but the lithium bond is hardly affected. In the trimers containing F^?, the H bond is more dominant than the Be(Mg) bond, whereas the Be(Mg) bond is more dominant in the halogen- and lithium-bonded analogues. On the other hand, the Be(Mg) bond makes the major contribution to the energetic stability of all of the trimers containing H₂O.     

Synthesis,crystal structure and spectral characteristics of highly fluorescent chalcone-based coumarin in solution and in polymer matrix

A new coumarin chalcone 3-((2E)-3-(2-hydroxyphenyl) prop-2-enoyl)-4-hydroxy-2(H)-chromen-2-one was synthesized using the Claisen Schmidt reaction by the condensation of 3-acetyl-4-hydroxycoumarin and 2-hydroxybenzaldehyde using a mild organic base. This novel compound was characterized by ¹H NMR, FT-IR and UV–vis spectroscopy. Single crystal X-ray diffraction investigation at low temperature (T=120 K) shows that this compound exhibits an intramolecular O3–H…O hydrogen bond, the coumarin ring and the phenyl group are nearly coplanar and the crystal packing is stabilized by intermolecular O3–H…O contacts and π–π stacking interactions. This ortho-hydroxyphenyl-4-hydroxycoumarin chalcone exhibits a strong blue-green emission under visible light excitation at 470 nm. The fluorescence behaviors of this compound doped in poly(methyl methacrylate) (PMMA) were investigated.