Electrolyte Effects on Charge Transport Behavior of [Os(bpy)2(PVP)10Cl]Cl and [Ru(bpy)2(PVP)10Cl]Cl Redox Polymers in Ultra‐Thin Films of Polyions

Metallopolymer films have important applications in electrochemical catalysis. The alternate electrostatic layer‐by‐layer method was used to assemble films of [Ru(bpy)₂(PVP)₁₀Cl]Cl (denoted as ClRu‐PVP) and [Os(bpy)₂(PVP)₁₀Cl]Cl (ClOs‐PVP) metallopolymers onto pyrolytic graphite electrodes. Film thickness estimated by quartz crystal microbalance was 6–8 nm. The effects of pH, electrolyte species and concentration on the electrochemical properties of these electroactive polymers were studied using cyclic voltammetry (CV). Behavior in various electrolytes was compared. Also the mass changes within the ultra‐thin film during redox of Os^2+/3+ were characterized by in situ electrochemical quartz crystal microbalance (EQCM). The results indicate rapid reversible electron transfer, and show that both ClRu‐PVP and ClOs‐PVP have compact surface structures while ClOs‐PVP is a little denser than ClRu‐PVP. Although hydrogen ions do not participate in the chemical reaction of either film, the movement of Na⁺ cation and water accompanies the redox process of ClOs‐PVP films.     

Enhanced third‐order nonlinear optical properties determined in thin films using the Z‐scan technique: bis(μ‐4,4′‐oxydibenzoato)bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine)cobalt(II)]

π‐Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4′‐Phenyl‐2,2′:6′,2′′‐terpyridine (PTP) is an important N‐heterocyclic ligand involving π‐conjugated systems, however, studies concerning the third‐order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co^II complex, bis(μ‐4,4′‐oxydibenzoato)‐κ³O,O′:O′′;κ³O′′:O,O′‐bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine‐κ³N,N′,N′′)cobalt(II)], [Co₂(C₁₄H₈O₅)₂(C₂₁H₁₅N₃)₂], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co^II cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry‐related monodentate 4,4′‐oxydibenzoate (ODA²⁻) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)]²⁺ units are bridged by ODA²⁻ ligands to form a ring‐like structure. The third‐order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z‐scan technique. The title compound shows a strong third‐order NLO saturable absorption (SA), while PTP exhibits a third‐order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is −37.3 × 10⁻⁷ m W⁻¹, which is larger than that (8.96 × 10⁻⁷ m W⁻¹) of PTP. The third‐order NLO susceptibility χ⁽³⁾ values are calculated as 6.01 × 10⁻⁸ e.s.u. for (1) and 1.44 × 10⁻⁸ e.s.u. for PTP.     

Organophosphine/phosphite‐stabilized silver(I) complexes bearing N‐acetylbenzamide ligand: synthesis,characterization and potential application in metal organic chemical vapor deposition

New N‐silver(I) acetylbenzamide complexes of type L_n?AgNC₉H₈O₂ (L = PPh₃; n = 1, 2a; n = 2, 2b; n = 3, 2c; L = P(OEt)₃; n = 1, 2d; n = 2, 2e; n = 3, 2f) were prepared. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³C{H} NMR, ³¹P{H} NMR and IR spectroscopy, respectively. The molecular structure of 2b has been determined by X‐ray single‐crystal analysis in which the silver atom is in a distorted tetrahedral geometry and crystallizes as cis–trans. New N‐silver(I) acetylbenzamide complexes have a four‐membered ring, which could influence their chemical and physical properties and modulate volatility. Metal organic chemical vapor deposition experiments were carried out successfully at 400°C and 450°C using 2e as precursor for the deposition of silver films, respectively. The high‐purity silver film obtained at 400°C is dense and homogeneous. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and optical characterization of photoactive poly(2‐phenoxyethyl acrylate) copolymers containing azobenzene units,prepared by frontal polymerization using novel ionic liquids as initiators

2‐Phenoxyethyl acrylate (2‐PEA) was polymerized alone and in the presence of an azobenzene comonomer derived from Disperse Red‐1, N‐ethyl‐N‐(2‐hydroxyethyl)‐4‐(4‐nitrophenylazo)aniline (MDR‐1), by using the frontal polymerization technique. Two novel ionic liquids, recently synthesized by us, were used as initiators: tetrabutylphosphonium persulfate (TBPPS) and trihexyltetradecylphosphonium persulfate (TETDPPS). Even if their concentrations were smaller than those found when benzoyl peroxide and terbutylperoxy neodecanoate were used, these compounds gave rise to stable propagating polymerization fronts characterized by relatively low maximum temperatures and good velocities. Moreover, at variance to these latter, TBPPS and TETDPPS prevent bubble formation, thus allowing the use of the obtained materials in optical applications. The obtained polymers were characterized by infrared spectroscopy (FTIR), their thermal properties were determined by differential scanning calorimetry, and their optical properties were studied by absorption spectroscopy in the UV–vis region. Finally, the nonlinear optical (NLO) properties of the 2‐PEA/MDR‐1 copolymers obtained with TBPPS and TETDPPS were performed according to the Z‐Scan technique with prepared film samples. It has been proven that samples with higher MDR‐1 content (0.05 mol %) exhibited outstanding cubic NLO activity with negative NLO refractive coefficients around n₂ = ?1.7 × 10^?3 esu. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Crystal growth in alumina/poly(ethylene terephthalate) nanocomposite films

The crystal growth and morphology in 150‐nm‐thick PET nanocomposite thin films with alumina (Al₂O₃) nanoparticle fillers (38 nm size) were investigated for nanoparticle loadings from 0 to 5 wt %. Transmission electron microscopy of the films showed that at 1 wt % Al₂O₃, the nanoparticles were well dispersed in the film and the average size was close to the reported 38 nm. Above 2 wt % Al₂O₃, the nanoparticles started to agglomerate. The crystal growth and morphological evolution in the PET nanocomposite films kept at an isothermal temperature of 217 °C were monitored as a function of the holding time using in situ atomic force microscopy. It was found that the crystal nucleation and growth of PET was strongly dependent on the dispersed particles in the films. At 1 wt % Al₂O₃, the overall crystal growth rate of PET lamellae was slower than that of the PET homopolymer films. Above 2 wt % Al₂O₃, the crystal growth rate increased with nanoparticle loading because of heterogeneous nucleation. In addition, in these PET nanocomposite thin films, the Al₂O₃ nanoparticles induced preferentially oriented edge‐on lamellae with respect to the surface, which was not the case in unfilled PET as determined by grazing‐incidence X‐ray diffraction. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 747–757, 2007     

Bis(5,7‐dimethyl‐8‐hydroxyquinolinato)platinum(II) Complex for Efficient Organic Heterojunction Solar Cells

Organic photovoltaic (OPV) cells using metal(II) (Pt, Pd, Cu, and Ni) chelates of 8‐hydroxyquinoline (Hq) or 5,7‐dimethyl‐8‐hydroxy‐quinoline (HMe₂q) as an electron donor were fabricated by vacuum deposition. The bis(5,7‐dimethyl‐8‐hydroxyquinolinato)platinum(II) [Pt(Me₂q)₂]‐based OPVs showed the best performance with an open voltage (V_OC) of 0.42 V, a short circuit current density (J_SC) of 14.8 mA cm^?2, and a maximum power conversion efficiency (η_P) of 2.4 %. The X‐ray single‐crystal structures together with the grazing incidence X‐ray diffraction (GIXRD) data of thin film samples reveal that the peripheral methyl substituent(s) and platinum(II) ion are essential for the high degree of film crystallinity resulting in improved performance of the as‐fabricated field‐effect transistors (FETs) and OPV cells.     

Thin Films that Consist of CuO Mesocrystal Nanosheets: An Application of Microbial‐Mineralization‐Inspired Approaches to Thin‐Film Formation

Thin films of copper oxides can be synthesized on substrates by using approaches that are inspired by microbial mineralization processes. In nature, precipitates of manganese and iron oxides with controlled oxidation states and crystal phases are produced through biomineralization by microorganisms. We have previously reported microbial‐mineralization‐inspired approaches that are comprised of direct and intermediate routes for the controlled syntheses of transition‐metal oxides. Herein, these approaches are applied to the thin‐film formation and coating of copper oxides and a related compound with controlled crystal phases and morphologies. Thin films of CuO, Cu₂O, and Cu₂(OH)₃Cl were selectively synthesized by using direct or intermediate routes. Notably, CuO mesocrystal nanosheets formed a thin film over the whole of the substrate. The resultant CuO mesocrystal nanosheets showed enhanced properties for the electrochemical detection of dopamine. This study shows the potential applicability of microbial‐mineralization‐inspired approaches to thin‐film coatings.     

Synthesis and characterization of main‐chain NLO oligomers and polymer that contain 4‐dialkylamino‐ 4′‐(alkylsulfonyl)azobenzene chromophores

An ω‐amino carboxylic acid monomer that contained a nonlinear optical (NLO) chromophore was prepared by a convergent synthesis. Strategies for selective protection/deprotection of the amino and carboxylic acid functionalities were developed. The protected monomer, 4‐[N‐(4‐benzyloxycarbonyl)butyl‐N‐methylamino]‐4′‐[2″,5″‐bis(decyloxy)‐4″‐(phthalimidomethyl)benzylsulfonyl]azobenzene, could be deprotected selectively or sequentially to give HOOC‐monomer‐N‐phthaloyl, benzyl‐OOC‐monomer‐NH₂, or HOOC‐monomer‐NH₂. Sequential synthesis was performed to yield main‐chain NLO dimers and tetramers. This was accomplished by selective deprotection and dicyclohexylcarbodiimide coupling. The HOOC‐monomer‐NH₂ was polymerized by treatment with diphenylphosphoryl azide to give a main‐chain NLO polyamide. The monomer, dimer, tetramer, and polymer NLO materials were characterized by ¹H, ¹³C, IR, and UV–visible spectroscopy as well as by gel permeation chromatography, differential scanning calorimetry, and elemental analysis. The NLO properties of these materials were measured. Thin films of the oligomers and polymer were prepared by spin casting on indium‐tin oxide coated glass. The second‐order NLO properties of the oligomers and polymer thin films were studied by in situ corona poling/second‐harmonic generation and attenuated total reflection methods. The optimal poling temperatures were significantly lower than the melting temperatures or glass‐transition temperatures of the oligomers and polymer. The poling efficiency increased in the following order: monomer, oligomers, and polymer. An electro‐optic coefficient of 4 pm/V at 1.06 μm was obtained for the polymer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 546–559, 2000     

NLO‐X (X = I–III): New Gaussian basis sets for prediction of linear and nonlinear electric properties

New adjusted Gaussian basis sets are proposed for first and second rows elements (H, B, C, N, O, F, Si, P, S, and Cl) with the purpose of calculating linear and mainly nonlinear optical (L–NLO) properties for molecules. These basis sets are new generation of Thakkar‐DZ basis sets, which were recontracted and augmented with diffuse and polarization extrabasis functions. Atomic energy and polarizability were used as reference data for fitting the basis sets, which were further applied for prediction of L–NLO properties of diatomic, H₂, N₂, F₂, Cl₂, BH, BF, BCl, HF, HCl, CO, CS, SiO, PN, and polyatomic, CH₄, SiH₄, H₂O, H₂S, NH₃, PH₃, OCS, NNO, and HCN molecules. The results are satisfactory for all electric properties tested; dipole moment (µ), polarizability (α), and first hyperpolarizability (β), with an affordable computational cost. Three new basis sets are presented and called as NLO‐I (ADZP), NLO‐II (DZP), and NLO‐III (VDZP). The NLO‐III is the best choice to predict L–NLO properties of large molecular systems, because it presents a balance between computational cost and accuracy. The average errors for β at B3LYP/NLO‐III level were of 8% for diatomic molecules and 14% for polyatomic molecules that are within the experimental uncertainty. © 2014 Wiley Periodicals, Inc.     

Organophosphine/phosphite‐stabilized silver(I) complexes bearing N‐hydroxysuccinimide ligand: synthesis,solid state structure and their potential use as MOCVD precursors

Six organophosphine/phosphite‐stabilized silver(I) N‐hydroxysuccinimide complexes of type [C₄H₄NO₃Ag?L_n] (L = PPh₃; n = 1, 2a; n = 2, 2b; L = P(OEt)₃; n = 1, 2c; n = 2, 2 d; L = P(OMe)₃; n = 1, 2e; n = 2, 2f) were prepared. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³ C{¹H} NMR and IR spectroscopy, respectively. The molecular structure of 2b has been determined by X‐ray single‐crystal analysis in which the silver atom is in a distorted tetrahedral geometry. An interstitial methanol solvent molecule is hydrogen bonded to the oxygen atom of N‐hydroxysuccinimide molecule. Complex 2f was used to deposit silver films by metal‐organic chemical vapor deposition (MOCVD) for the first time. The silver film obtained at 480 °C is dense and homogeneous, which is composed of many well‐isolated, granular particulates spreading all over the substrate surface. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and Photoluminescence Properties of Silver(I) Metal‐Organic Polymers with Nanochannels Based on 2‐Sulfoterephthalic Acid and Di(pyridin‐2‐yl)amine Ligands

Two new silver(I) 3D coordination polymers, namely [Ag₃(2‐stp)(dpa)]_n ( 1 ) and {[Ag₂(2‐stp)(H₂O)]?Hdpa}_n ( 2 ) (2‐NaH₂stp=sodium 2,5‐dicarboxysulfonate, dpa=di(pyridine‐2‐yl)amine) were synthesized. The complexes were characterized by elemental analysis, FT‐IR spectra, thermogravimetric analyses (TGA), and single‐crystal X‐ray diffraction. In complex 1 , three neighboring Ag ions are bridged by N‐ and O‐atom, forming a 3D coordination network. The molecular structure of 2 is cation? anion species, forming 3D host? guest supramolecular network with the [Hdpa]⁺ cations encapsulated in the nanochannels. The photoluminescence properties of the complexes were also investigated in the solid state at room temperature.     

Synthesis and nonlinear optical properties of methacrylate polymers based on 2‐[4‐(N‐methyl,N‐hydroxyethylamino)phenylazo]‐phenyl‐6‐nitrobenzoxazole chromophore

Methacrylate polymers containing different molar contents of nonlinear optical (NLO) active molecular segments based on 2‐[4‐(N‐methyl,N‐hydroxyethylamino)phenylazo]‐phenyl‐6‐nitrobenzoxazole chromophores were synthesized, and their phase behavior and second‐order NLO properties were investigated. Polymers containing 6–17 mol % chromophore segments allowed the preparation of amorphous and optically clear thin films. Some mesomorphic structuration was exhibited by a polymer with 33 mol % chromophoric units. However, this feature did not prevent the possibility of investigating the NLO properties. Nonlinear resonance‐enhanced d₃₃ coefficients were determined by second harmonic generation experiments on spin‐coated, corona‐poled thin films at λ = 1064 nm. Values ranging from 40 to 60 pm/V were measured with increasing chromophore molar contents. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1841–1847, 2003     

A non‐linear optical crystal,Cd3Zn3(BO3)4

The title compound, tricadmium trizinc tetraborate, Cd₃Zn₃(BO₃)₄, is a new non‐linear optical (NLO) crystal and its structure has been determined by single‐crystal X‐ray diffraction. This compound is composed of planar [BO₃]³⁻ groups sharing O atoms with CdO₄ or ZnO₄ tetrahedra. The BO₃ triangles are located on threefold axes and are arranged with nearly the same orientation. The Cd and Zn atoms are disordered on the same site in the proportion 1:1. A strong second harmonic generation of Nd:YAG laser radiation (λ = 1064 nm) has been observed for a crystal of the title compound.     

Mono and Poly‐nuclear Silver(I) Complexes with Thiosaccharin and Triphenylphosphine. Synthesis,Spectroscopic and Structural Characterization of Thiosaccharinato‐bis(triphenylphosphine)silver(I) and Tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

The reaction of Ag₆(tsac)₆ ( 1 ) (tsac = thiosaccharinate anion) with triphenylphosphine gives rise to the already reported [Ag(tsac)(PPh₃)₃] complex ( 2 ) and to two new silver‐thiosaccharinate‐phosphine complexes, [Ag(tsac)(PPh₃)₂] ( 3 ) and [Ag₄(tsac)₄(PPh₃)₄] ( 4 ) (PPh₃= triphenylphosphine). Spectroscopic characterization was carried out using IR, UV‐Visible and NMR techniques and confirmed by single crystal X‐ray diffraction. In each complex a singular coordination mode for the thiosaccharinate ligand is observed. The most important features of the different coordination modes of the thionates are discussed. Compound 3 crystallizes in monoclinic system, space group Pn, with a = 11.2293(3) Å, b = 12.7282(3) Å, c = 13.6056(4) Å, β = 94.985(2)°, Z = 2; while crystals of compound 4 are monoclinic, space group P2₁/n, a = 15.024(3) Å, b = 14.681(3) Å, c = 21.914(4) Å, β = 95.31(3)°, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal‐planar arrangements, AgP₂S in 3 and AgS₂P in 4 .     

Synthesis,crystal structure,absorption properties,photoelectric behavior of organic–inorganic hybrid (CH3NH3)2CoCl4

Lead‐free and organic–inorganic hybrid (CH₃NH₃)₂CoCl₄ [(MA)₂CoCl₄] single crystal and thin film are prepared. The single crystal diffraction data of (MA)₂CoCl₄ are assigned to monoclinic, P2(1)/C space group (7.6590 × 12.6908 × 10.89350 Å, 90.0 × 96.5320 × 90.000). The absorption edge of (MA)₂CoCl₄ reaches 730 nm. The band gap for (MA)₂CoCl₄ is determined to be approximately 1.63 eV. To the best of our knowledge, this is the first study on (MA)₂CoCl₄ for optoelectronic applications. A low‐cost photodetector based on (MA)₂CoCl₄ thin film is efficient under different monochromatic light from 330 nm to 400 nm with different chopping frequencies (1.33–60 Hz). The strongest photoresponse (I_on ? I_off) is under 330 nm monochromatic light with 1.33 Hz according to our optimal condition. The calculational results by density functional theory show that the narrow valence bands and conduction bands are derived from the 3p orbitals of Cl and 3d orbitals of Co.     

Magnetic properties of a new cobalt hydrogen vanadate with a dumortierite‐like structure: Co13.5(OH)6(H0.5VO3.5)2(VO4)6

The magnetic properties of a novel cobalt‐based hydrogen vanadate, Co_13.5(OH)₆(H_0.5VO_3.5)₂(VO₄)₆, are reported. This new magnetic material was synthesized in single‐crystal form using a conventional hydrothermal method. Its crystal structure was determined from single‐crystal X‐ray diffraction data and was also characterized by scanning electron microscopy. Its crystal framework has a dumortierite‐like structure consisting of large hexagonal and trigonal channels; the large hexagonal channels contain one‐dimensional chains of face‐sharing CoO₆ octahedra linked to the framework by rings of VO₄ tetrahedra, while the trigonal channels are occupied by chains of disordered V₂O₄ pyramidal groups. The magnetic properties of this material were investigated by DC magnetic measurements, which indicate the occurrence of antiferromagnetic interactions.     

Synthesis and characterization of nano-silica gel aged under microwave radiation from white sandstone

Double perovskite La₂NiMnO₆ thin film was successfully prepared on (001)-oriented 0.7 wt% Nb-doped SrTiO₃ single crystal substrate by chemical solution deposition method. The microstructures as well as properties were investigated. The results show that the derived thin film is an admixture of Ni/Mn ordering, and two ferromagnetic transitions are observed with Curie temperatures of 289 and 110 K, respectively. A crossover from positive to negative magnetodielectric effect is observed near room temperature. The success preparation of La₂NiMnO₆ thin film by chemical solution deposition will provide a useful method to deposit double perovskite multiferroic thin films with low-cost.     

Tetrazine Chromophore‐Based Metal–Organic Frameworks with Unusual Configurations: Synthetic,Structural, Theoretical,Fluorescent, and Nonlinear Optical Studies

Three unusual three‐dimensional (3D) tetrazine chromophore‐based metal–organic frameworks (MOFs) {(Et₄N)[WS₄Cu₃(CN)₂(4,4′‐pytz)_0.5]}_n ( 1 ), {[MoS₄Cu₄(CN)₂(4,4′‐pytz)₂] ? CH₂Cl₂}_n ( 2 ), and {[WS₄Cu₃(4,4′‐pytz)₃] ? [N(CN)₂]}_n ( 3 ; 4,4′‐pytz=3,6‐bis(4‐pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X‐ray diffraction, gel permeation chromatography, steady‐state fluorescence, and thermogravimetric analysis; their identities were confirmed by single‐crystal X‐ray diffraction studies. MOF 1 possesses the first five‐connected M/S/Cu (M=Mo, W) framework with an unusual 3D (4⁴?6⁶) topology constructed from T‐shaped [WS₄Cu₃]⁺ clusters as nodes and single CN^?/4,4′‐pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (4²⁰?6⁸) topology, in which the bridging 4,4′‐pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel‐shaped [WS₄Cu₃]⁺ clusters with a non‐interpenetrating honeycomb‐like framework and a heavily distorted “ACS” topology. Steady‐state fluorescence studies of 1 – 3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1 – 3 were investigated by using a Z‐scan technique with 5 ns pulses at λ=532 nm. The Z‐scan experimental results show that the π‐delocalizable tetrazine‐based 4,4′‐pytz ligands contribute to the strong third‐order NLO properties exhibited by 1 – 3 . Time‐dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.     

Synthesis,characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-(4-nitrophenyl)imidazo[4,5-f] [1,10]phenanthroline

Two novel Ru^II complexes [Ru(phen)₂(PNOPH)]²⁺ and [Ru(dmp)₂ (PNOPH)]²⁺ (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, PNOPH = 2-(4-nitrophenyl)imidazo-[4,5-f][1,10]phenanthroline) and their deprotoned complexes were synthesized and characterized by ES–MS, ¹H - n.m.r, u.v.–vis. and electrochemistry. The crystal structure of the deprotonated complex [Ru(dmp)₂ (PNOP)][ClO₄] · CH₃CN was determined by means of X-ray single crystal diffraction. Nonlinear optical properties of the Ru^II complexes were investigated by Z-scan techniques in DMF solution, and all of them exhibited both NLO absorption and self-defocusing effect. The corresponding effective NLO susceptibilities |³ | of the complexes are 2.39 × 10^-12–5.80 × 10^-12 esu.     

Quantum‐chemical,IR, NMR,and X‐ray diffraction studies on 2‐(4‐chlorophenyl)‐1‐methyl‐ 1H‐benzo[d]imidazole

The title molecule, 2‐(4‐chlorophenyl)‐1‐methyl‐1H‐benzo[d]imidazole (C₁₄H₁₁ClN₂), was prepared and characterized by ¹H NMR, ¹³C NMR, IR, and single‐crystal X‐ray diffraction. The molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) ¹H and ¹³C NMR chemical shift values of the title compound in the ground state have been calculated by using the Hartree‐Fock (HF) and density functional theory (DFT/B3LYP) method with 6‐31G(d) basis sets, and compared with the experimental data. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and GIAO ¹H and ¹³C NMR chemical shifts show good agreement with experimental values. The energetic behavior of the title compound in solvent media has been examined using B3LYP method with the 6‐31G(d) basis set by applying the Onsager and the polarizable continuum model (PCM). Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, and nonlinear optical (NLO) properties of the title compound were investigated by theoretical calculations. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011