Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(Ⅱ) complexes

The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(Ⅱ) complexes were carried out using density functional theory(DFT).The results indicate that these complexes have large second-order nonlinear optical(NLO) responses.Specially,complex 6b has a maximal first hyperpolarizability βtot value.The first hyperpolarizabilities can be tuned by changing the ancillary ligand,introducing electron-acceptor group NO2 and/or increasing π-conjugation on phenanthroline.Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer(ILCT),while the complexes in series b exhibit metal-to-ligand charge transfer(MLCT) and ligand-to-ligand charge transfer(LLCT) transition at relatively low-energy absorptions.     

具有不同生色团的Pt（Ⅱ）配合物二阶非线性光学性质的DFT研究

采用密度泛函理论B3LYP／LANL2DZ方法,对实验合成的含有不同生色团的Pt（Ⅱ）配合物的电子性质和二阶非线性光学（NLO）效应进行计算分析。结果表明：配合物中二苯基啡咯啉部分表现出给电子的性质,金属Pt（Ⅱ）在配合物内起到平衡电荷的作用。对配合物lb～6b与配合物a进行比较发现,配合物1b-5b的βvec值比配合物a的成βvec值增大,而配合物6b的βvec值比配合物a的风值减小。7个配合物中前线分子轨道能级差越小的配合物,它的βvec值越大,同时配合物更深层占有轨道与空轨道之间的电子跃迁对二阶NLO效应有明显的贡献。     

Pt(Ⅱ), Pd(Ⅱ) and Ni(Ⅱ) Complexes Binding to the N(7) Position of Guanine: Influence on the Guanine and Watson-crick GC Base Pair

Comprehensive ab initio calculations were performed on the coordination of Pt(Ⅱ),Pd(Ⅱ) and Ni(Ⅱ) adducts to the N(7) of guanine and guanine-cytosine (GC) base pair at the DFT level. The fully optimized geometries of the metal complexes were obtained and the stabilization energies of the interaction between metal adducts and nucleobase were calculated with B3LYP method by using 6-31^* basis set for the light atom. While the effective core potential (ECP) is used for metal cation. The results show that both cispalladium and cisnickel cause similar geometric changes of the base pair as cisplatin. For the coordination of metal adducts to guanine, platinum adduct possesses the highest stabilization energy; but the interaction between metal-guanine and cytosine for nickel is larger than that for platinum and palladium. It is worthy to note that hydrolysis effect can also cause significant changes in H-bonds.     

Computational study on second-order nonlinear optical (NLO) properties of a novel class of two-dimensional Λ- and W-shaped sandwich metallocarborane-containing chromophores

We systematically investigate the linear optical properties and the static second-order nonlinear optical (NLO) properties on a series of two-dimensional (2D) D-π-A-π-D/A-π-D-π-A sandwich metallocarborane-containing molecules with density functional theory (DFT). It can be found that the substitution effect has an influence on the electronic absorption and NLO responses of the 2D molecules. For example, the ${\beta }_{vec}$ value is sensitive to the substitution from amino (–NH₂) to nitryl (–NO₂); the angle between the two A–D branches significantly affects the dipole moment and ${\beta }_{vec}$ value. In addition, time-dependent DFT calculations and the analysis of major molecular orbitals predict that the sandwich metallocarborane acts as an electron donor better than electron acceptor. Furthermore, the two strong synchronized charge transfer (CT) coming from the two branches and p–π (B_2p–C≡C) conjugation contributes to the second-order polarizabilities in our studied systems.     

DFT Studies on Second-order Nonlinear Optical Response of Ir(C∧N)2(pic)Complexes

Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.     

含吡啶配体过渡金属(M=Cr(0),Mn(Ⅰ),Fe(Ⅱ),Co(Ⅲ))配合物二阶NLO性质的DFT研究

采用密度泛函理论（DFT）B3LYP／6-31G（d）方法对含吡啶配体的过渡金属（M=Cr（0）,Mn（Ⅰ）,Fe（Ⅱ）,Co（Ⅲ））配合物的几何构型进行优化,进一步结合有限场（FF）方法,计算其二阶NLO系数．结果表明,吡啶配体和中心金属原子之间的配位键键长随中心金属价态升高逐渐减小,增加吡啶配体的共轭链长度使极化率变得更大．共轭桥的增长有利于分子内电荷转移,对应体系的二阶NLO系数较大．     

Synthesis and characterization of μ-oxamido copper(Ⅱ)-iron(Ⅱ) heterobinuclear complexes with an antiferromagnetic exchange interaction

Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-2     

Theoretical studies on the spectroscopic properties and the substituent effects of pyridyl triazole Os(Ⅱ) complexes

To explore the spectroscopic properties of pyridyl triazole Os(Ⅱ) complexes and how the substituent effects affect the spectroscopic properties of [Os(ptz)2L2] (L=PH3; ptzH=(2-pyridyl)-1,2,4-triazole) (1), [Os(bptz)2L2] (bptzH=3-tert-butyl-5-(2-pyridyl)-1,2,4-triazole) (2), [Os(fptz)2L2] (fptzH=3- (trifluoreomethyl)- 5-(2-pyridyl)-1,2,4-triazole) (3), and [Os(fbtz)2L2] (fbtzH=3-(trifluoreomethyl)-5-(4-tert-butyl- 2-pyridyl)-1,2, 4-triazole) (4), the density functional theory (DFT) method at the B3LYP level ...     

Synthesis,Crystal Structure and Luminescent Mechanochromism of a Square-planar Pt(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative

A new square-planar platinum(Ⅱ) complex, [Pt(Me3SiC≡Cphen)(C≡CC6H4Cl-3)2](1), was synthesized by using 3-trimethylsilylethynyl-1,10-phenanthroline(Me3SiC≡Cphen) and 3-chlorophenylacetylene ligands, and its structure was characterized by single-crystal X-ray crystallography. 1 crystallizes in triclinic, space group P1 with a = 6.9524(5), b = 12.7796(11), c = 17.5846(10) ?, α = 78.484(5), β = 88.700(5), γ = 75.600(6)°, V = 1482.23(19) ?3, Z = 2, C33H24Cl2N2 PtSi, Mr = 742.62, Dc = 1.664 g/cm3, F(000) = 724, μ(Mo Ka) = 4.979 mm-1, R = 0.0369 and wR = 0.0786. In 1, adjacent molecules along the a axis are stacked in a columnar structure through π···π interactions, and such neighboring columnar structures are connected with each other by C–H···π hydrogen bonds to form a 2D supramolecular network. 1 exhibits reversible luminescence mechanochromic property with the luminescence red shift in a range of ca. 146~182 nm. Extremely large red-shifts of luminescence spectra suggest that luminescent mechanochromic property of 1 is due to the formation of aggregate via Pt–Pt interaction during the mechanical grinding. Based on this property, a simple device was developed and used for rewritable data storage.     

Synthesis and molecular modeling study of Cu(Ⅱ) complexes derived from 2-(diphenylmethylene)hydrazinecarbothioamide derivatives with cholinesterase inhibitory activities

Thiosemicarbazones of 2-amino-5-chlorobenzophenone and 3-aminobenzophenone（L¹-L⁴） have been synthesized and their Cu（Ⅱ） complexes（1-4） were afforded via coordination with cupric chloride.All these compounds were characterized by UV-vis and IR spectroscopy together with CHN elemental analysis.NMR spectroscopy was also applied to characterize the ligands.In vitro chohnesterase inhibitory assays for the complexes（1-4） showed IC₅₀ values less than 10μmol/L,with complex 1 exhibiting the most activity,IC₅₀=2.15μmol/L and 2.16μmol/L for AChE and BuChE,respectively. Molecular modeling simulation revealed the binding interaction template for complex 1 with the AChE and BuChE receptors.In DPPH assay,the complexes also showed more in vitro antioxidant activities in comparison to their parent ligands.     

A study on some macrocyclic bicopper(Ⅱ) complexes as the model compounds of superoxide dismutase

24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds of superoxide dismutase (SOD),the relationship between their SOD activities and properties of bridging ligands and redox potentials of copper(Ⅱ) were studied.     

Synthesis, DNA-binding and photocleavage studies of ruthenium(Ⅱ) complexes [Ru(btz)_3]~(2+) and [Ru(btz)(dppz)_2]~(2+)

Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm,...     

Syntheses,Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr(Ⅱ) complex, [Sr(Hsip)(H2O)](1, NaH2sip = 5-sulfoisophthalic acid monosodium), has been synthesized by solvothermal reaction of Sr CO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Singlecrystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr(Ⅱ) ion in 1. The coordination geometry of Sr(Ⅱ) is a distorted tetragonal anti-prism. The whole Hsip2- ligand performs a μ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.     

Synthesis,Crystal Structure and Magnetic Behavior of a Novel Cd(Ⅱ) Complex with Four Nitroxide Radicals

A novel diamagnetic-metal Cd(Ⅱ) complex with four nitroxide radicals[Cd(IM4Py)4Cl2](IM4Py=2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) was synthesized and characterized by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction.The complex crystallized in triclinic space group P1 with a=0.93285(14) nm,b=1.16827(18) nm,c=1.3660(2) nm,α=112.759(2)°,β=104.524(2)°,γ=92.008(3)°,V= 1.3143(3) nm3,Z=1,Dc=1.335 g/cm3,the final R1=0.0423 and wR2=0.1009.In the title complex,each Cd(Ⅱ) ion adopting a distorted octahedral geometry is coordinated by two Cl-anions and four pyridyl-N atoms from four IM4Py ligands.The magnetic measurements show the weak antiferromagnetic interactions between the nitroxide radicals.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Nickel(Ⅱ) Complex with 2-Pyridinecarboxyic Acid and 4,4′-Bipyridine Ligands

A new metal-organic coordination polymer [Ni[(2-pya)2(4,4′-bipy)]n·6nH2O (2-pya = 2-pyridinecarboxylic acid, 4,4′-bipy = 4,4′-pyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.5642(19), c = 10.7118(18), V = 5453.8(11) 3, C22H28N4NiO10, Mr = 567.19, Dc = 1.382 g/cm3, μ(MoKα) = 0.769 mm-1, F(000) = 2368, Z = 8, the final R = 0.0572 and wR = 0.1254 for 1401 observed reflections (I > 2σ(I)). It exhibits a one-dimensional chain-like structure by mixed ligands of 2-pyridinedicarboxylic acid and 4,4′-pyridine.     

Synthesis and properties of the copper(Ⅱ) complexes with stable radical

Four novel copper(Ⅱ) complexes have been synthesized,namely Cu(hfac)2NITPhNO2 (1),Cu(hfac)2NITPhCH3 (2),Cu(pfpr)2NITPhNO2,(3) and Cu(Pfpr)2NITPhCH3 (4),where hfac= hexafluoro-acetylacetonate,pfpr=pentafluoropropionate,NITR.=2-R-4,4,5,5-tetraniethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide.(R=4-nitrophenyl,4-methylphenyl).These complexes were rharicter-ized by elemental analyses,IR,electronic spectra and molar conductance.The temperature-dependent magnetic susceptibility of complexes 1 and 3 have been studied in the 4 300 K range,giving I he exchange integral J=10.56 cm-1 for complex 1 and J =-30.9 cm-1 for complex 3.     

Synthesis and Characterization of Nickel(Ⅱ) and Copper(Ⅱ) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes,Ni(salen) (salen=(1R,2R)-(-)-diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene) 1 and Cu(salen) 2,have been synthesized and characterized by IR,microanalysis,TGA,powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P2_12_12 with Z=4. For 1,α= 12.082(2),b = 15.447(3),c = 18.784(4)(A),V= 3505.7(12) (A)~3,M_r = 731.50,D_c = 1.386 g/cm~3,μ= 0.606 mm~(-1),F(000)=1544,the final GOOF=1.043,R=0.0496 and wR=0.1248 for 4791 observed reflections with Ⅰ> 2σ(Ⅰ). For 2,α=12.181(2),b=15.501(3),c=18.877(4)(A),V= 3564.3(12)(A)~3,M_r=736.33,Dc = 1.372 g/cm~3,μ=0.665 mm~(-1),F(000)=1548,the final GOOF= 1.062,R=0.0575 and wR=0.1508 for 4562 observed reflections with Ⅰ> 20(Ⅰ). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.     

7,10,12顶点Fe(Ⅱ)碳硼烷夹心配合物NLO性质的DFT研究

采用密度泛函理论(DFT)CAM-B3LYP方法对系列7,10,12顶点Fe(Ⅱ)碳硼烷与1,2,4,5-Me4C6H2(dur1),1,2,3,4-Me4C5H(dur2)形成的夹心配合物的非线性光学(NLO)性质进行了计算分析.结果表明,Fe(Ⅱ)碳硼烷的顶点数和硝基的取代位置影响分子的几何构型,从而影响分子的NLO性质;Fe(Ⅱ)碳硼烷夹心配合物的偶极矩与极化率随碳硼烷的顶点数增加而增大;10顶点Fe(Ⅱ)碳硼烷分子的前线分子轨道能级差较小,其第一超极化率βtot值大于12及7顶点Fe(Ⅱ)碳硼烷分子;硝基与Fe(Ⅱ)处于对位时,其βtot值大于未取代分子;硝基与Fe(Ⅱ)处于邻位时,βtot值较未取代分子小;在此类Fe(Ⅱ)碳硼烷夹心配合物中,碳硼烷既可以作电子给体,也可以作电子受体.     

Synthesis,structures and magnetic properties of a series of polynuclear copper(Ⅱ)-lanthanide(Ⅲ) complexes assembled with carboxylate and hydroxide ligands

Heterometallic copper(Ⅱ)-lanthanide(Ⅲ) complexes have been made with a variety of exclusively O-donor ligands including betaines (zwitterionic carboxylates) and chloroac-etate,which are dinuclear CuLn,tetranuclear Cu2Ln2,pen-tanuclear Cu2Ln2,and octadecanuclear Cu12Ln6 complexes.Hie results show that subtle changes in both the carboxylates and acidity of the reaction solution can cause drastic changes in the structures of the products.Magnetic studies exhibit that shielding of the Ln3 4f electrons by the outer shell electrons is very effective to preclude significant coupling interaction between the Ln3 4f electrons and Cu2 3d electrons in either a mono-atomic hydroxide-bridged,or a carboxylate-bridged system.     

Synthesis and Crystal Structure of Zn(Ⅱ) Complex with Tridentate Ligand N-(2-Hydroxy-1-naphthylidene)-L-serine

A new Zn(Ⅱ) complex, [Zn(L)2(H2O)2], where H2L = N-(2-hydroxy-l-naphthylidene)-L-serine, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 13.669(2), b = 6.4657(9), c =31.463(5) (A), β = 98.010(2)°, V = 2753.6(7) (A)3, Z = 8, Mr = 358.64, Dc = 1.730 g/cm3, F(000) =1472,μ(MoKa) = 1.814 mm-1, the final R = 0.0355 and wR = 0.0706. The Zn(Ⅱ) atom adopts a square-pyramidal geometry coordinated by the tridentate ligand and two water molecules.Intermolecular hydrogen bonds link the complex molecules into a two-dimensional layer.