[WS3Cu2]簇基超分子框的组装、结构及其三阶非线性光学响应

将二(4-吡啶)硫烷(L₁)、4,4''-二(4-吡啶)二苯甲酮(L₂)分别与(Et₄N)(Tp*WS₃)(A)(Tp*=三(3,5-二甲基吡唑)氢合硼酸根)和[Cu (MeCN)₄]PF₆进行反应,得到2个W/Cu/S簇基超分子化合物[Tp*WS₃Cu₂(L₁)]₂(PF6)2·2MeCN·2CHCl₃(1·2MeCN·2CHCl₃)和[Tp*WS₃Cu₂(L₂)(MeCN)]₂(PF₆)₂·4MeCN (2·4MeCN)。对配合物1·2MeCN·2CHCl₃和2·4MeCN分别进行了单晶X射线衍射、核磁、质谱、红外、紫外可见和元素分析表征。单晶X射线衍射分析表明,它们是由2个L₁/L₂配体连接2个[Tp*WS₃Cu₂]⁺簇核形成的阳离子型簇基超分子框。核磁氢谱和高分辨电喷雾离子化质谱(HRESI-MS)证明它们在溶液中具有一定的稳定性。并利用Z扫描技术测试了超分子化合物1·2MeCN·2CHCl₃和2·4MeCN溶液的三阶非线性光学特性,测试结果表明它们的三阶非线性光学响应强于前驱体A。     

簇合物[WS4Ag3(PPh3)3{S2P(OCH2Ph)3}]的合成、晶体结构及非线性光学性质

本文用(NH₄)₂WS₄，Ag[S₂P(OCH₂Ph)₂]和PPh₃为原料合成了簇合物[WS₄Ag₃(PPh₃)₃{S₂P(OCH₂Ph)₃}]，并得到了晶体。晶体属正交晶系，空间群为P2₁2₁2₁，晶胞参数a=1.32370(4)nm，b=1.34427(4)nm，c=3.83246(11)nm。X-射线单晶结构测定结果表明它具有巢状分子结构，配体(PhCH₂O)₂PS₂^-(简称dtp)的两个S原子中的一个硫原子仅与一个金属原子配位，另一个硫原子则同时与两个金属原子配位。簇合物的非线性光学性质用脉宽8ns激光在532nm波长进行了研究。该化合物表现为一定的光学吸收和强的自聚焦效应，其三阶非线性吸收系数α₂=1.50×10^-10m·W^-1，折射系数n₂=2.45×10^-11esu。     

原子簇化合物[WS4Cu3Br(bipy)2]的晶体结构和非线性光学性质

The title cluster compound [WS₄Cu₃Br(bipy)₂] has been synthesized by the reaction of (NH₄)₂[WS₄]， CuBr and 2，2′-bipy in DMF solution. Single crystal X-ray diffraction data show that the compound has a nest-shaped structure. Nonlinear optical properties (NLO) of the cluster were investigated by a Z-scan technique with a pulsed laser at 532nm. The cluster exhibits the strong NLO absorption and a self-defocusing effect (effective non-linear absorption coefficient， α₂^eff=7.3×10^-11mW^-1; effective non-linear refractive index， n₂^eff=3.9×10^-11esu) when measured in a 6.0×10^-4mol·dm^-3 DMF solution. CCDC： 200397.     

(ZnS)6~12团簇三阶非线性光学性质的理论研究

在TDDFT/Lanl2DZ+6-31G*水平下对(ZnS)6~12半导体团簇的三阶非线性光学性质进行了计算, 并用态求和(SOS)方法得到静态三阶宏观极化率χ(3)和0~2.5 eV范围内输入光子能量对三阶微观极化率γ的动态行为. 结果表明, (ZnS)6~12的χ(3)值比其它半导体团簇的略好. 且(ZnS)7和(ZnS)11分别在1.6和2.0 eV处出现了很大的γ值, 为-2.38×10-33和1.26×10-33 esu. 在此输入光子能量处激发, 它们将会产生很强的三阶非线性光学效应.     

新颖五核Mo/Cu/S簇合物[MoOS3Cu4(α-MePy)6Br2]的合成及晶体结构

杂核金属含硫簇合物具有丰富的结构,在生物化学、催化和非线性光学等方面显示了诱人的应用前景.近年来,我们主要从事用[MS4 ]2 - 和[Cp* MS3]- ( M=Mo,W)和Cu( ) ,Ag( )反应合成Mo( W) /Cu( Ag) /S簇合物并研究其非线性光学性质[1,2 ] .鉴于用硫代金属酸盐作前驱体合成M- Cu- Ag- S杂三核金属簇合物的工作鲜有报道[3] ,我们尝试用( NH4 ) 2 Mo OS3和Cu Br,Ag Br在α- Me Py中反应,希望得到Mo- Cu- Ag- S杂三核金属簇合物.但上述反应却形成了1个仅含Mo和Cu( )的五核簇合物[Mo OS3Cu4 (α- Me Py) 6 Br2 ],其所含的Mo S3…     

二茂铁基查尔酮衍生物的超快三阶非线性光学响应

合成三例二茂铁基查尔酮衍生物:1-二茂铁基-3-(5-溴噻吩-2-基)-2-丙烯-1-酮(1)、1-二茂铁基-3-(4-溴噻吩-2-基)-2-丙烯-1-酮(2)和1-二茂铁基-3-(5-氯噻吩-2-基)-2-丙烯-1-酮(3);采用1H NMR、13C NMR和HR-MS对化合物1～3进行了结构表征,并测定了其热学性质;运用密度泛函理论方法进行结构优化,并计算得到了它们的分子轨道能量和极化率;采用紫外-可见吸收光谱与Z-扫描技术(532nm,180fs)分别测定了三种化合物的线性和非线性光学性质。结果表明,化合物1～3的紫外吸收波长发生明显红移,且1的非线性吸收幅度、极化率和分子超极化率最大; 1、2和3均存在分子内电荷转移现象,表现出超快三阶非线性光学响应。     

金属团簇MoS4Cu4(SCN)2(NC5H5)6的皮秒光学非线性特性和光限幅特性研究

由于激光技术的快速发展，新型超快可调谐波长的高功率激光器更多的在民用和军事上应用。快速的非线性光学器件的需求越来越多。近10年，人们投入大量研究寻找超快光学非线性材料，同时寻找快速响应、高线性透过率和低非线性透过率以及高损伤阈值的光限幅材料，研究发现金属酞菁化合物、金属卟啉化合物以及富勒烯衍生物具有良好的光限幅效果和强的光学非线性特性。     

Cu2ZnSnS4纳米晶的制备及其三阶非线性光学性能的研究

以乙酰丙酮铜、醋酸锌、二氯亚锡、油胺和硫粉为前驱体,采用one-pot法合成出了单分散的Cu2ZnSnS4(CZTS)纳米晶.所得样品采用X射线粉末衍射仪(XRD),能量色散谱仪(EDS),透射电子显微镜(TEM),高分辨透射电子显微镜(HRTEM),光电子能谱仪(XPS),紫外-可见光谱仪(UV-vis)和Z-扫描(Z-scan)技术对其结构组成、形貌、性能等进行了表征.结果表明:所获得的产物为四方相结构的六边形CZTS纳米颗粒,直径约为10 nm.计算出尺寸大小为10 nm,13 nm的纳米晶的三阶非线性光学折射率γ(-1.08×10-15,-9.08×10-17 m2·W-1),三阶非线性光学吸收系数β(6.5×10-9,3.69×10-11 m·W-1)以及三阶非线性光学极化率χ(3)(1.49×10-9,4.35×10-10 esu).并探讨了CZTS纳米晶可能的形成机理,及引起三阶光学非线性发生变化的原因。     

两个二茂铁基查尔酮衍生物的合成及超快三阶非线性光学响应

合成两种新颖的含二茂铁基团的查尔酮衍生物：1-二茂铁基-3-(4-叔丁基苯基)丙烯酮(a)和1-二茂铁基-3-联苯基丙烯酮(b),经₁H NMR、₁₃C NMR、HR-MS对其结构进行了表征;测定了该两化合物的热力学性质;采用量子化学方法计算了它们的分子轨道能量和极化率,给出了轨道电子云图;采用紫外-可见吸收光谱和Z-扫描技术测定了其线性和非线性光学性质。结果表明：与原料相比,化合物a和b的紫外吸收明显增加,且b的吸收波长更长;化合物a和b均存在分子内电荷转移现象,表现出超快三阶非线性光学响应。     

若干有机非线性光学材料的分子设计及 三阶非线性光学性质的理论研究①

On the basis of INDO/SCI method, using sum-over-states (SOS) method,the third-order nonlinear optical susceptibilities γ(-ω;ω,-ω,ω) and γ(0;0,0,0)of a series of organic molecules have been calculated. The effects of molecular backbone, donor substitutes, the number of thiophene-ring (namely the conjugated molecular length dependence) on the γ have been studied.     

Synthesis, crystal structure and third-order non-linear optical property of heterobimetallic cluster compound [MoOICu3S3(2,2′-bipy)2]

Nest-shaped cluster [MoOICu₃S₃(2,2′-bipy)₂] (1) was synthesized by the treatment of (NH₄)₂MoS₄, CuI, (n-Bu)₄NI, and 2,2′-bipyridine (2,2′-bipy) through a solid-state reaction. It crystallizes in monoclinic space group P2₁/n, a=9.591(2) Å, b=14.820(3) Å, c=17.951(4) Å, β=91.98(2)°, V=2549.9(10) ų, and Z=4. The nest-shaped cluster was obtained for the first time with a neutral skeleton containing 2,2′-bipy ligand. The non-linear optical (NLO) property of [MoOICu₃S₃(2,2′-bipy)₂] in DMF solution was measured by using a Z-scan technique with 15 ns and 532 nm laser pulses. The cluster has large third-order NLO absorption and the third-order NLO refraction, its ₂ and n₂ values were calculated as 6.2×10⁻¹⁰ and −3.8×10⁻¹⁷ m² W⁻¹ in a 3.7×10⁻⁴ M DMF solution.     

Heterobimetallic Cluster-Based Coordination Polymers: Assembly,Structures and Third-Order Nonlinear Optical Properties

Reactions of (NH₄)₂WS₄ with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN)₄]PF₆/bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et₄N]₂[WS₄Cu₄(μ-CN)₂(μ-I)₂]}_n ( 1 ), [WS₄Cu₄(μ-CN)₂(bppa)₂]_n ( 2 ) and {[WS₄Cu₄(bppa)₄](PF₆)₂}_n ( 3 ), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a “sql” topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare “reo” topology. Compounds 1 – 3 in DMF exhibited different third-order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self-focusing effect.     

Heterometallic copper(Ⅱ) vanadates: synthesis,crystal structures and third-order nonlinear optical properties

Three polymeric heterometallic clusters with 1D, 2D, and 3D frameworks, constructed from a cyclic vanadate {V4O12}4-building block and three geometric constraint ligands, were synthesized by a one-pot self-assembly reaction. Z-scan experiments demonstrated that all the three cluster polymers have large hyperpolarizability γ values. TD-DFT calculations afforded insight into the electronic transitions and spectral characterization of these novel NLO molecular materials.     

Synthesis, crystal structure, and nonlinear optical properties of Bi2Cu5B4O14

Bi₂Cu₅B₄O₁₄ crystallizes in the noncentrosymmetric triclinic space group P1 (No. 1) with cell parameters a=10.1381(11) Å, b=9.3917(11) Å, c=3.4566(4) Å, α=105.570(2)°, β=92.275(2)°, γ=107.783(2)°, Z=1 and R₁=0.0401 and wR₂=0.0980. It is a layered structure that is built up from sheets of rectangular CuO₄ and trigonal BO₃ groups. The sheets are connected by infinite chains of edge shared BiO₆ polyhedra that intersect the bc plane at an angle slightly greater than 90°. The second-harmonic generation efficiency of Bi₂Cu₅B₄O₁₄, using 1064 nm radiation, is about one half times that of KH₂PO₄.     

CuO-SiO_2和Cu_2O-SiO_2薄膜的制备及其光学性能

以CuSO_4·5H_2O和正硅酸乙酯为前驱体,配制了稳定透明的Cu~(2+)-SiO_2复合溶胶电解液。采用电化学-溶胶凝胶方法,在恒电位-0.9 V下得到Cu-SiO_2复合膜,该复合薄膜分别在250和450℃的热处理后得到Cu_2O-SiO_2和CuO-SiO_2复合薄膜。采用XRD、SEM/EDX和台阶仪表征了复合薄膜的组成、形貌和厚度;采用紫外-可见光谱和Z扫描技术研究了复合薄膜的线性和三阶非线性光学性能。结果表明Cu2O-SiO_2和CuO-SiO_2复合薄膜中的Cu含量、Cu的形态(如Cu_2O、CuO)及Cu_2O或CuO颗粒大小影响薄膜的光学带隙和三阶非线性光学性能,2种薄膜的光学带隙分别是2.67和2.54 eV,三阶非线性极化率χ(3)分别为2.31×10~(-6)和1.36×10~(-6) esu。     

CuO-SiO2和Cu2O-SiO2薄膜的制备及其光学性能

以CuSO₄·5H₂O和正硅酸乙酯为前驱体,配制了稳定透明的Cu²⁺-SiO₂复合溶胶电解液。采用电化学-溶胶凝胶方法,在恒电位-0.9 V下得到Cu-SiO₂复合膜,该复合薄膜分别在250和450℃的热处理后得到Cu₂O-SiO₂和CuO-SiO₂复合薄膜。采用XRD、SEM/EDX和台阶仪表征了复合薄膜的组成、形貌和厚度;采用紫外-可见光谱和Z扫描技术研究了复合薄膜的线性和三阶非线性光学性能。结果表明Cu₂O-SiO₂和CuO-SiO₂复合薄膜中的Cu含量、Cu的形态（如Cu₂O、CuO）及Cu₂O或CuO颗粒大小影响薄膜的光学带隙和三阶非线性光学性能,2种薄膜的光学带隙分别是2.67和2.54 eV,三阶非线性极化率χ^（3）分别为2.31×10^-6和1.36×10^-6 esu。     

TA on Mo(W)/Cu(Ag)/S clusters derived with [Cp*MS3]- Kinetics of [PPh4]2[Cp*WS3(CuBr)3]2 and [PPh4]2[Cp*MoS3(CuBr)3]2

Thermal analysis on two new heterometallic sulfide clusters, [PPh4]2[WS3(CuBr)3]2 and [PPh4]2[MoS3(CuBr)3]2 (where PPh4=tetraphenyl phosphonium, =pentamethylcyclopenta- dienyl), was carried out using a simultaneous TG-DTA unit in an atmosphere of flowing nitrogen and at various heating rates. Supplemented using EDS method, their thermal behavior and properties, together with the composition of their intermediate product, were examined and discussed in connection with their distinctive molecular structure as a dianion, which provided some theoretically and practically significant information. Both clusters decomposed in a two-step mode, but without a stable new phase composed of Mo/W-Cu-S formed during their decomposition process as we expected. Based on TG-DTG data, four methods, i.e. Achar-Brindley-Sharp, Coats-Redfern, Kissinger and Flynn- Wall-Ozawa equation, were used to calculate the non-isothermal kinetic parameters and to determine the most probable mechanisms. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a discrete decanuclear iodocuprate(I) [Cu10H2I16] with [Ni(phen)3] as a template

The title compound [Ni^II(phen)₃]₂[Cu₁₀H₂I₁₆] 1 (phen=1,10-phenanthroline, C₁₂H₈N₂) was hydrothermally synthesized from a simple reaction of CuI-NiCl₂·6H₂O-phen·H₂O-H₂O. X-ray analysis revealed that it consists of NiN₆²⁺ core cation and decanuclear iodocuprate(I) anion together with two dissociative H⁺ ions. In anionic unit, the discrete decanuclear iodocuprate(I) is formed by crystallographically independent five monovalent copper atoms and eight iodine atoms via an inversion center. There exist two types of Cu(I) coordination sites; only one copper(I) atom is in a highly distorted triangular planar site, and the other four copper(I) atoms display the tetrahedral geometries. It deserves to be noted that four types of bridging modes of I⁻ ions in which two are ordinary μ₂- and μ₃-bonding modes can be found. But the other two are the rectangle planar geometry and the novel μ₄-bridge like an “umbrella”, and both of them are rather rare in the halocuprates(I). Compound 1 was crystallized in triclinic space group with a=11.6861(17), b=14.590(2), c=14.649(2) Å, α=76.370(2), β=70.830(2), γ=81.320(3)^o, R=0.075, and was characterized by elemental analysis, IR spectrum and UV-VIS spectrum. The third-order non-linear optical property of 1 was also investigated and the compound exhibits the reverse saturable absorption and self-defocusing performance.