A comprehensive study on the photophysical and non-linear optical properties of thienyl-chalcone derivatives.

The impact of the substitutional position of the chorine atom on the non-linear optical (NLO) response of chalcone derivatives is reported in this paper. Two thienyl-chalcone derivatives, (E)-3-(2,4-dichloro-phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3A25D2) and (E)-3-(2,6-dichloro-phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3A25D4), are synthesized, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The photophysical and third-order NLO properties of 3A25D2 and 3A25D4 were investigated experimentally and computationally. The third-order NLO properties of 3A25D2 and 3A25D4 dissolved in N,N-dimethylformamide (DMF) were studied using Z-scan technique with 800 nm, 70 femtosecond (fs) pulses, and 532 nm continuous wave (CW) laser excitation. Closed aperture data recorded with fs pulses revealed positive non-linearity of both the compounds, while a strong negative non-linearity was observed in the CW regime. Open aperture data revealed that both the compounds exhibit positive non-linear absorption in fs pulsed and CW domains. Several wave function analysis methods, such as the inter-fragment charge transfer (IFCT) analysis, hole-electron analysis, (hyper)polarizability density analysis, and decomposition of the (hyper)polarizability contribution by numerical integration, were carried out to study the optical properties and charge transfer mechanism. In addition, the influence of the medium (liquid and crystalline) and external field wavelength on the optical properties of the two molecules were analyzed. Thermal and electronic contributions toward NLO properties were studied experimentally. The theoretically calculated cubic hyperpolarizability γ(-ω; ω, ω, -ω) in liquid for 3A25D2 and 3A25D4 were 4.69 × 10-34 and 2.68 × 10-34 esu, whereas the corresponding femtosecond regime Z-scan results gave 4.35 × 10-34 and 3.78 × 10-34 esu, respectively.

Benzofuranyl Esters: Synthesis, Crystal Structure Determination, Antimicrobial and Antioxidant Activities.

A series of five new 2-(1-benzofuran-2-yl)-2-oxoethyl 4-(un/substituted)benzoates 4(a-e), with the general formula of C8H5O(C=O)CH2O(C=O)C6H4X, X = H, Cl, CH3, OCH3 or NO2, was synthesized in high purity and good yield under mild conditions. The synthesized products 4(a-e) were characterized by FTIR, ¹H-, (13)C- and ¹H-(13)C HMQC NMR spectroscopic analysis and their 3D structures were confirmed by single-crystal X-ray diffraction studies. These compounds were screened for their antimicrobial and antioxidant activities. The tested compounds showed antimicrobial ability in the order of 4b < 4a < 4c < 4d < 4e and the highest potency with minimum inhibition concentration (MIC) value of 125 µg/mL was observed for 4e. The results of antioxidant activities revealed the highest activity for compound 4e (32.62% ± 1.34%) in diphenyl-2-picrylhydrazyl (DPPH) radical scavenging, 4d (31.01% ± 4.35%) in ferric reducing antioxidant power (FRAP) assay and 4a (27.11% ± 1.06%) in metal chelating (MC) activity.

Impact of Diverse Parameters on the Physicochemical Characteristics of Green-Synthesized Zinc Oxide-Copper Oxide Nanocomposites Derived from an Aqueous Extract of Garcinia mangostana L. Leaf.

Compared to conventional metal oxide nanoparticles, metal oxide nanocomposites have demonstrated significantly enhanced efficiency in various applications. In this study, we aimed to synthesize zinc oxide-copper oxide nanocomposites (ZnO-CuO NCs) using a green synthesis approach. The synthesis involved mixing 4 g of Zn(NO3)2·6H2O with different concentrations of mangosteen (G. mangostana) leaf extract (0.02, 0.03, 0.04 and 0.05 g/mL) and 2 or 4 g of Cu(NO3)2·3H2O, followed by calcination at temperatures of 300, 400 and 500 °C. The synthesized ZnO-CuO NCs were characterized using various techniques, including a UV-Visible spectrometer (UV-Vis), photoluminescence (PL) spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, X-ray powder diffraction (XRD) analysis and Field Emission Scanning Electron Microscope (FE-SEM) with an Energy Dispersive X-ray (EDX) analyzer. Based on the results of this study, the optical, structural and morphological properties of ZnO-CuO NCs were found to be influenced by the concentration of the mangosteen leaf extract, the calcination temperature and the amount of Cu(NO3)2·3H2O used. Among the tested conditions, ZnO-CuO NCs derived from 0.05 g/mL of mangosteen leaf extract, 4 g of Zn(NO3)2·6H2O and 2 g of Cu(NO3)2·3H2O, calcinated at 500 °C exhibited the following characteristics: the lowest energy bandgap (2.57 eV), well-defined Zn-O and Cu-O bands, the smallest particle size of 39.10 nm with highest surface area-to-volume ratio and crystalline size of 18.17 nm. In conclusion, we successfully synthesized ZnO-CuO NCs using a green synthesis approach with mangosteen leaf extract. The properties of the nanocomposites were significantly influenced by the concentration of the plant extract, the calcination temperature and the amount of precursor used. These findings provide valuable insights for researchers seeking innovative methods for the production and utilization of nanocomposite materials.

Biological and cytoselective anticancer properties of copper(II)-polypyridyl complexes modulated by auxiliary methylated glycine ligand.

A series of ternary copper(II)-1,10-phenanthroline complexes with glycine and methylated glycine derivatives, [Cu(phen)(aa)(H(2)O)]NO(3)·xH(2)O 1-4 (amino acid (aa): glycine (gly), 1; DL: -alanine (DL: -ala), 2; 2,2-dimethylglycine (C-dmg), 3; sarcosine (sar), 4), were synthesized and characterized by FTIR, elemental analysis, electrospray ionization-mass spectra (ESI-MS), UV-visible spectroscopy and molar conductivity measurement. The determined X-ray crystallographic structures of 2 and 3 show each to consist of distorted square pyramidal [Cu(phen)(aa)(H(2)O)](+) cation, a nitrate counter anion, and with or without lattice water, similar to previously reported structure of [Cu(phen)(gly)(H(2)O)]NO(3)·1½H(2)O. It is found that 1-4 exist as 1:1 electrolytes in aqueous solution, and the cationic copper(II) complexes are at least stable up to 24 h. Positive-ion ESI-MS spectra show existence of only undissociated [Cu(phen)(aa)](+) species. Electron paramagnetic resonance, gel electrophoresis, fluorescence quenching, and restriction enzyme inhibition assay were used to study the binding interaction, binding affinity and selectivity of these complexes for various types of B-form DNA duplexes and G-quadruplex. All complexes can bind selectively to DNA by intercalation and electrostatic forces, and inhibit topoisomerase I. The effect of the methyl substituents of the coordinated amino acid in the above complexes on these biological properties are presented and discussed. The IC(50) values (24 h) of 1-4 for nasopharyngeal cancer cell line HK1 are in the range 2.2-5.2 µM while the corresponding values for normal cell line NP69 are greater than 13.0 µM. All complexes, at 5 µM, induced 41-60 % apoptotic cell death in HK1 cells but no significant cell death in NP69 cells.

2-Amino-3-nitro-benzoic acid.

The title compound, C(7)H(6)N(2)O(4), is approximately planar (r.m.s. deviation = 0.026 Šfor the 13 non-H atoms). The mol-ecular structure is stabilized by intra-molecular N-H⋯O hydrogen bonds, which generate S(6) ring motifs. In the crystal, mol-ecules are linked via inter-molecular N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional network.

(2-Chloro-4-nitro-benzoato)(methanol)triphenyl-tin(IV).

In the title complex, [Sn(C(6)H(5))(3)(C(7)H(3)ClNO(4))(CH(4)O)], the five-coordinate Sn(IV) atom exists in a trigonal-bipyramidal environment, formed by a monodentate carboxyl-ate group, three phenyl rings and a methanol mol-ecule. The axial sites are occupied by the O atoms of the methanol mol-ecule and the carboxyl-ate group, while the equatorial plane is formed by the C atoms of three phenyl rings. The benzene ring of the 2-chloro-4-nitro-benzoate ligand makes dihedral angles of 66.18 (7), 74.71 (7) and 77.39 (7)° with respect to the three phenyl rings. In the crystal, the mol-ecules are linked via inter-molecular O-H⋯O and C-H⋯O hydrogen bonds into a column along the b axis.

(2-Amino-3-nitro-benzoato-κO)triphenyl-tin(IV).

The asymmetric unit of the title compound, [Sn(C(6)H(5))(3)(C(7)H(5)N(2)O(4))], consists of two independent mol-ecules. In each mol-ecule, the four-coordinated Sn(IV) atom exists in a distorted tetra-hedral geometry and two intra-molecular N-H⋯O hydrogen bonds with S(6) ring motifs are present. In one mol-ecule, the benzene ring of the 2-amino-3-nitro-benzoate ligand makes dihedral angles of 42.74 (11), 89.66 (13) and 53.04 (10)° with the three phenyl rings. The corresponding dihedral angles for the other mol-ecule are 6.29 (11), 66.55 (11) and 62.33 (10)°. In the crystal, a weak inter-molecular C-H⋯π inter-action and a π-π stacking inter-action with a centroid-centroid distance of 3.5877 (12) Šare observed.

Octa-butylbis[µ(2)-4-(diethyl-amino)-benzoato-κO:O']bis-[4-(diethyl-amino)-benzoato-κO]di-µ(3)-oxido-tetra-tin(IV).

The asymmetric unit of the title complex, [Sn(4)(C(4)H(9))(8)(C(11)H(14)NO(2))(4)O(2)], consists of two crystallographically independent half-mol-ecules. The other halves are generated by crystallographic inversion centers. In each tetra-nuclear mol-ecule, both of the two independent Sn atoms are five-coordinated, with distorted trigonal-bipyramidal SnC(2)O(3) geometries. One Sn atom is coordinated by two butyl groups, one O atom of the benzoate anion and two bridging O atoms, whereas the other Sn atom is coordinated by two butyl groups, two O atoms of the benzoate anions and a bridging O atom. All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. Weak intra-molecular C-H⋯O hydrogen bonds stabilize the mol-ecular structures. In one mol-ecule, two of the butyl groups and the bridging benzoate anion are each disordered over two positions.

Bis(µ(2)-2-amino-5-nitro-benzoato)bis-(2-amino-5-nitro-benzoato)octa-butyldi-µ(3)-oxido-tetra-tin(IV).

In the title complex, [Sn(4)(C(4)H(9))(8)(C(7)H(5)N(2)O(4))(4)O(2)], all four Sn(IV) atoms are five-coordinated with distorted trigonal-bipyramidal SnC(2)O(3) geometries. Two Sn(IV) atoms are coordin-ated by two butyl groups, one benzoate O atom and two bridging O atoms, whereas the other two Sn(IV) atoms are coordinated by two butyl groups, two benzoate O atoms and a bridging O atom. All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. In the crystal, mol-ecules are linked into a two-dimensional layer parallel to the ab plane by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds and further stabilized by a π-π inter-action [centroid-centroid distance = 3.6489 (11) Å]. Intra-molecular N-H⋯O and C-H⋯O hydrogen bonds stabilize the mol-ecular structure. Two of the butyl groups are each disordered over two sets of sites with site-occupancy ratios of 0.510 (4):0.490 (4) and 0.860 (5):0.140 (5).

catena-Poly[[triphenyl-tin(IV)]-µ-5-amino-2-nitro-benzoato-κO:O].

The title compound, [Sn(C(6)H(5))(3)(C(7)H(5)N(2)O(4))](n), forms polymeric chains along [010]. The Sn(IV) ion is five-coordinated in a distorted trigonal-bipyramidal geometry by two monodentate carboxyl-ate groups and three phenyl rings. The axial sites are occupied by the O atoms of two symmetry-related carboxyl-ate groups [O-Sn-O = 170.88 (3)°]. The benzene ring of the 5-amino-2-nitro-benzoate ligand forms dihedral angles of 82.92 (6), 81.10 (6) and 83.54 (6)° with respect to the three phenyl rings. In the crystal, the chains are linked by inter-molecular N-H⋯O and weak C-H⋯O inter-actions into a three-dimensional network. The crystal structure is further stabilized by weak inter-molecular C-H⋯π inter-actions.

(4-Chloro-3-nitro-benzoato)triphenyl-tin(IV).

In the title compound, [Sn(C(6)H(5))(3)(C(7)H(3)ClNO(4))], the four-coordinate Sn(IV) atom exists in a distorted tetra-hedral geometry, formed by a monodentate carboxyl-ate group and three phenyl rings. The conformation is stabilized by an intra-molecular C-H⋯O hydrogen bond, which generates an S(5) ring. The aromatic ring of the 4-chloro-3-nitro-benzoate ligand makes dihedral angles of 75.64 (12), 64.37 (12) and 2.97 (12)° with the three phenyl ligands. The O atoms of the nitro group are disordered over two sets of sites in a 0.817 (5):0.183 (5) ratio. In the crystal, mol-ecules are linked via inter-molecular C-H⋯O hydrogen bonds into chains running parallel to [010].

Poly[[aquadi-µ(3)-malonato-hexaphenyl-ditin(IV)] acetone solvate].

The asymmetric unit of the title polymeric complex, {[Sn(2)=(C(6)H(5))(6)(C(3)H(2)O(4))(H(2)O)]·C(3)H(6)O}(n), comprises of two Sn cations, one malonate anion and a non-coordinating acetone solvent mol-ecule. Both crystallographically independent Sn cations are five-coordinated by two O and three C atoms in a distorted trigonal-bipyrimidal geometry. One of the Sn cations is bridged by the malonate units, affording polymeric chains which run along [001]. Weak intra-molecular C-H⋯π inter-actions stabilize the mol-ecular structure. In the crystal structure, adjacent chains are inter-connected by inter-molecular O-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional supra-molecular structure. A weak inter-molecular C-H⋯π inter-action is also observed.

Bis(µ(2)-4-amino-3-nitro-benzoato)bis-(4-amino-3-nitro-benzoato)octa-butyldi-µ(3)-oxido-tetra-tin(IV).

The tetranuclear molecules of the title compound, [Sn(4)(C(4)H(9))(8)(C(7)H(5)N(2)O(4))(4)O(2)], reside on a crystallographic inversion center. Both the two independent Sn atoms are five-coordinate, with distorted trigonal-bipyramidal geometries. One Sn atom is coordinated by two O atoms of the carboxyl-ate anions, one bridging O atom and two butyl groups and the other Sn atom is coordinated by an O atom of the carboxyl-ate anion, two bridging O atoms and two butyl groups. All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. The mol-ecular structure is stabilized by intra-molecular N-H⋯O hydrogen bonds. In the crystal, pairs of inter-molecular bifurcated acceptor N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into chains along [10]. Weak inter-molecular C-H⋯π and π-π inter-actions [centroid-centroid distance = 3.713 (2) Å] are also observed.

Octa-butyl-bis-(µ(2)-2-chloro-5-nitro-benzoato)bis-(2-chloro-5-nitro-benzoato)di-µ(3)-oxido-tetra-tin(IV).

The title complex, [Sn(4)(C(4)H(9))(8)(C(7)H(3)ClNO(4))(4)O(2)], is a cluster formed by a crystallographic inversion center around the central Sn(2)O(2) ring. Both of the two independent Sn atoms are five-coordinated, with distorted trigonal-bipyramidal SnC(2)O(3) geometries. One Sn atom is coordinated by two butyl groups, one O atom of the benzoate anion and two bridging O atoms, whereas the other Sn atom is coordinated by two butyl groups, two O atoms of the benzoate anions and a bridging O atom. The O atoms of the bridging benzoate anion are disordered over two sites with an occupancy ratio of 0.862 (12):0.138 (12). One of the butyl groups coordinated to the Sn(2)O(2) ring is disordered over two sites with an occupancy ratio of 0.780 (8):0.220 (8), whereas both of the two butyl groups coordinated to the other Sn atom are disordered over two sites with occupancy ratios of 0.788 (5):0.212 (5) and 0.827 (10):0.173 (10). All the butyl groups are equatorial with respect to the SnO(3) trigonal plane. In the crystal, complex mol-ecules are stacked down [010] with weak inter-molecular C-H⋯π inter-actions stabilizing the crystal structure.

[3-(Dimethyl-amino)benzoato]triphenyl-tin(IV).

In the title compound, [Sn(C(6)H(5))(3)(C(9)H(10)NO(2))], the Sn atom is coordinated by three phenyl groups and a carboxyl-ate anion in a distorted tetra-hedral geometry. An intra-molecular C-H⋯O inter-action forms an S(7) ring motif. The dihedral angles between the benzoate group and the other three phenyl rings are 76.94 (8), 66.82 (8) and 42.34 (9)°. The crystal structure is further stabilized by inter-molecular C-H⋯π inter-actions.

Octa-n-butyl-1κC,2κC,3κ,4κC-bis-(µ-2,3-dibromo-propionato)-1:2κO:O',3:4κO:O'-bis-(2,3-dibromo-propionato)-1κO,3κO-di-µ(3)-oxido-1:2:4κO:O:O,2:3:4κO:O:O-tetra-tin(IV).

In the centrosymmetric tetra-nuclear title complex, [Sn(4)(C(4)H(9))(8)(C(3)H(3)Br(2)O(2))(4)O(2)], one of the two independent Sn atoms is five-coordinated by one O atom of the carboxyl-ate anion, two bridging O atoms and two n-butyl groups in a C(2)SnO(3) distorted trigonal bipyramidal geometry. The other Sn atom also has a distorted trigonal bipyramidal geometry, being coordinated by two O atoms of two carboxyl-ate anions, one bridging O atom and two butyl groups. An inter-esting feature of the crystal structure is the short Sn⋯O [2.756 (4) Å] and O⋯O [2.608 (3) Å] inter-actions. The -BrCH(2)-CHBr- segments of the two carboxyl-ate anions are disordered over two positions [site occupancies of 0.60 (1)/0.40 (1) and 0.53 (2)/0.47 (2)]. Weak non-directional C-H⋯O inter-actions lead to the formation of infinte chains along the a axis; other weak inter-molecular C-H⋯π inter-actions are also present.

Two closely related 2-(benzo-furan-2-yl)-2-oxoethyl benzoates: structural differences and C-H⋯O hydrogen-bonded supra-molecular assemblies.

The compounds 2-(1-benzo-furan-2-yl)-2-oxoethyl 2-nitro-benzoate, C17H11NO6 (I), and 2-(1-benzo-furan-2-yl)-2-oxoethyl 2-amino-benzoate, C17H13NO4 (II), were synthesized under mild conditions. Their mol-ecular structures were characterized by both spectroscopic and single-crystal X-ray diffraction analysis. The mol-ecular conformations of both title compounds are generally similar. However, different ortho-substituted moieties at the phenyl ring of the two compounds cause deviations in the torsion angles between the carbonyl group and the attached phenyl ring. In compound (I), the ortho-nitro-phenyl ring is twisted away from the adjacent carbonyl group whereas in compound (II), the ortho-amino-phenyl ring is almost co-planar with the carbonyl group. In the crystal of compound (I), two C-H⋯O hydrogen bonds link the mol-ecules into chains propagating along the c-axis direction and the chains are inter-digitated, forming sheets parallel to [20-1]. Conversely, pairs of N-H⋯O hydrogen bonds in compound (II) link inversion-related mol-ecules into dimers, which are further extended by C-H⋯O hydrogen bonds into dimer chains. These chains are inter-connected by π-π inter-actions involving the furan rings, forming sheets parallel to the ac plane.

Steric repulsion and supra-molecular assemblies via a two-dimensional plate by C-H⋯O hydrogen bonds in two closely related 2-(benzo-furan-2-yl)-2-oxoethyl benzoates.

2-(Benzo-furan-2-yl)-2-oxoethyl 2-chloro-benzoate, C17H11ClO4 (I), and 2-(benzo-furan-2-yl)-2-oxoethyl 2-meth-oxy-benzoate, C18H14O5 (II), were synthesized under mild conditions. Their chemical and mol-ecular structures were analyzed by spectroscopic and single-crystal X-ray diffraction studies, respectively. These compounds possess different ortho-substituted functional groups on their phenyl rings, thus experiencing extra steric repulsion force within their mol-ecules as the substituent changes from 2-chloro (I) to 2-meth-oxy (II). The crystal packing of compound (I) depends on weak inter-molecular hydrogen bonds and π-π inter-actions. Mol-ecules are related by inversion into centrosymmetric dimers via C-H⋯O hydrogen bonds, and further strengthened by π-π inter-actions between furan rings. Conversely, mol-ecules in compound (II) are linked into alternating dimeric chains propagating along the [101] direction, which develop into a two-dimensional plate through extensive inter-molecular hydrogen bonds. These plates are further stabilized by π-π and C-H⋯π inter-actions.

Crystal structure and Hirshfeld surface analysis of (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(2,4-di-fluoro-phen-yl)prop-2-en-1-one].

The asymmetric unit of the title compound, C24H14F4O2, comprises of one and a half mol-ecules; the half-mol-ecule is completed by crystallographic inversion symmetry. In the crystal, mol-ecules are linked into a three-dimensional network by C-H⋯F and C-H⋯O hydrogen bonds. Some of the C-H⋯F links are unusually short (< 2.20 Å). Hirshfeld surface analyses (dnorm surfaces and two-dimensional fingerprint plots) for the title compound are presented and discussed.

Three closely related (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(meth-oxy-phen-yl)prop-2-en-1-ones]: supra-molecular assemblies in one dimension mediated by hydrogen bonding and C-H⋯π inter-actions.

In the title compounds, (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(2-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (I), (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (II) and (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3,4-di-meth-oxy-phen-yl)prop-2-en-1-one], C28H26O6 (III), the asymmetric unit consists of a half-mol-ecule, completed by crystallographic inversion symmetry. The dihedral angles between the central and terminal benzene rings are 56.98 (8), 7.74 (7) and 7.73 (7)° for (I), (II) and (III), respectively. In the crystal of (I), mol-ecules are linked by pairs of C-H⋯π inter-actions into chains running parallel to [101]. The packing for (II) and (III), features inversion dimers linked by pairs of C-H⋯O hydrogen bonds, forming R22(16) and R22(14) ring motifs, respectively, as parts of [201] and [101] chains, respectively.