具有聚集诱导发光及机械变色特性的含Au(Ⅰ)化合物的设计、合成及性质研究

设计合成了两个含Au(I)的化合物1和2,利用核磁共振(NMR)、红外光谱(IR)、元素分析等对其结构进行了表征.通过对其在二甲亚砜(DMSO)/水体系或N,N-二甲基甲酰胺(DMF)/水体系中荧光光谱的研究,显示其在纯有机溶剂中没有荧光,而在混合体系中,水含量达到一定程度后,其荧光会显著增强.这表明化合物1和2均具有明显的聚集诱导发光性质.对化合物1和2的固体粉末进行研磨,其固体荧光会显著增强,而且将研磨后的样品暴露在有机溶剂蒸汽中一段时间后,荧光强度又会恢复到原来的强度.这表明化合物1和2均具有机械变色的性质.通过它们的X射线粉末衍射(XRD)测试发现,这两个化合物在研磨前后分子堆积态实现了从晶态到无定形态的转变.因此这两个化合物具有成为新型智能材料的潜质.     

含偶氮苯的双金属钌配合物的合成及性质研究

近几十年来,光致变色在实际中的应用日益增多,特别是有机发光材料在光信息存储、分子开关和其他的光学器件方面,有着广泛的发展前景并且已经取得了许多突出成就,引起了广泛的关注[1].而有机偶氮化合物在光作用前后,其化学结构能够发生改变,因此在光开关和高精密度的信息存储材料方面得到了很好的应用.将金属原子引入到具有光致变色性质的偶氮化合物中,特别是那些具有空d轨道的过渡金属和空f轨道的稀土金属.由于他们的价电子数变化多,并且分子结构特殊,材料性能可以在很大的范围内进行调变.同时这些金属配合物分子中大多都具有共轭的π键,可以发生分子内电子转移反应,引起价电荷的转移,因而这一类化合物在光电功能材料方面具有很大的发展前景[2].     

新型四炔模块苯炔前体高效构建咔唑类衍生物

采用卡迪奥-肖德凯维奇偶联反应合成了一系列的四炔类的化合物, 随后利用这些新型四炔模块苯炔前体高效地合成了一系列咔唑类衍生物. 此外, 银具有很好的催化活性, 当加入催化量的AgNO₃到反应体系中时, 通过一步反应能够获得同时含有咔唑环和吲哚环的多元杂环化合物. 更重要的是, 这些反应具有很高的产率. 此外, 这类反应的底物适用性是非常广的. 并且提出了涉及到AgNO₃催化的N-H插入反应的可能的机理.     

Asymmetric Synthesis and Crystal Structure of （-）-N-[（3R）-3-Cyclohexyl]-3-phenylpropananoyl]bornane-10,2-sultam

The title compound (-)-N-[(3R)-3-cyclohexyl]-3-phenylpropananoyl]bornane-10,2sultam (C 25 H 35 NO 3 S,M r=429.60),a derivative of camphorsultam,crystallizes in the monoclinic space group P2 1 /c with a=10.3301(7),b=19.4040(13),c=11.8106(8),β=100.5580(10)°,V=2327.3(3) 3,Z=4,D c=1.226 g/cm 3,λ=0.71073,μ(MoKα)=0.165 mm-1 and F(000)=928.X-ray diffraction analysis reveals that the six-membered ring of sultam shows a boat form (Fig.1).The planes constructed by (C(4),C(5),C(6),C(7)) and (C(7),C(8),C(9),C(4)) form a dihedral angle of 69.5°.The C(1)-C(2)-C(3) plane forms dihedral angles to the aforementioned planes of 89.8(1) and 85.9(3)°,respectively.And molecules are linked via hydrogen bonding (C-H···N/O) interactions.     

The time-resolved spectra of a crowned indolinospiroben-zopyran

The photochromic process of an indolinospiropyran with a crown ether fragment (BN-BIPS) was studied by nanosecond laser photolysis technique. The results show that quinonic merocyanine B was formed via an excited singlet state from BN-BIPS; in acetonitrile solution, the transient absorption of merocyanine B showed an obvious decay while a new transient absorption at 440nm (from isomer C) was observed simultaneously. The decay of merocyanine B and the formation of isomer C (at 440nm) were accelerated in the presence of alkali metal cation. In contrast, the formation of isomer C was not observed in spiropyran without a crown ether fragment: BIPS.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Crystal Structure of Copper（ Ⅱ）Complex with 3—Hydroxyl—1,5—diazaylo

Crystal structure of copper (II) complex with a new aminocarboxylate ligand, 3-hydroxyl-1, 5-diazacycloheptane-N,N-diacetate, C9H14CuN2O5.H2O, Mr=311.78 is reported. It crystallizes in orthorhombic Pna21 with a=13.340(4), b=8.127(1), c=10.583(4) , V=1147.2(7)3 , Z=4, Dc=1.805g/cm3, μ=19.287cm-1 (MoKα), F(000)=644. The final R and Rw are 0.049 and 0.065 for 888 observed reflections with I≥3σ(I). The result of X-ray structure determination shows that the Cu(Ⅱ) forms a planar complex with two oxygen atoms and two nitrogen atoms of the ligand.     

两个基于二噻吩乙烯结构单元双核钌乙烯配合物的合成, 表征和性质

合成了2个含二噻吩乙烯结构单元双核钌乙烯配合物[RuCl（CO）（PMe₃）₃]₂（μ-2,2’-（CH=CH）^2-DTE）（1a）和[RuCl（CO）（PMe₃）₃]₂（μ-2,5-（CH=CH）₂-DTE）（1b）,利用元素分析、红外、核磁共振谱和电化学对它们的结构进行了表征,X-射线单晶衍射分析表明,配合物1a晶体属单斜晶系,C2/c空间群,晶胞参数为：a=3.44575（6）nm,b=1.45945（2）nm,c=2.32191（5）nm,β=110.9770（10）°,V=10.9028（3）nm³,Z=8,D_c=1.467g·cm^-3,λ=0.071073nm,μ（MoKα）=0.956mm^-1,F（000）=4912。测定了它们光照前后的紫外-可见吸收光谱变化图,并对其光致变色性质进行了讨论。