含二苯并-18-冠-6和二苯并-14-冠-4的酰胺型液晶冠醚的合成

以4-[(4-正烷氧基联苯基)-4-碳酰氧基]苯甲酸、二氨基二苯并-18-冠-6和二氨基二苯并-14-冠-4为中间体, 通过溶液缩合反应, 合成了两个系列酰胺型液晶冠醚. 并用元素分析、核磁共振、红外光谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征. 随分子末端烷氧基碳原子数增加, 化合物4I, 4II, 6I和6II的熔点(T_m)和液晶态的清亮点(T_i)逐渐降低, 近晶相范围递增.     

端基含4个丁氧基苯介晶基元光致变色液晶树状物的合成、结构及液晶性研究

合成了周边含4个丁氧基偶氮苯介晶基元(M5)端基新的零代光致变色液晶树状物(D0),并用元素分析、核磁共振、基质辅助激光解吸飞行时间质谱、红外、紫外、偏光显微镜、差示扫描量热(DSC)和广角X射线衍射法(WAXD)表征.D0显示向列相,与M5相同,树状物相态由介晶基元相态所决定,D0的相行为:K138N147I145N118K.对零代(D0)、一代(D1)、二代(D2)和三代(D3)液晶树状物的清亮焓、清亮熵、熔化焓和熔化熵进行了比较.     

三代碳硅烷光致变色液晶树状物的光化学研究——端基含108个4-丁氧基偶氮苯介晶基元

报道了新化合物含108个丁氧基偶氮基元端基的三代(D3)碳硅烷光致变色液晶树状物在各溶液中的反-顺光异构化(光致变色)反应速率常数k_p, 光化学回复异构化正/逆反应速率常数k_t和k_c, 热回复异构化反应速率常数k_H, 光化学回复异构化反应平衡常数k_t/k_c, 活化能E, 异构化转换率及热回复异构化反应中的反-顺异构体组分比. D3的光致变色反应速率常数为10^－1 s^－1, 而含偶氮基元的光致变色液晶聚硅氧烷的光致变色反应速率常数为10^－8 s^－1, 因此, D3的光响应速度比后者快10⁷倍.     

N，N′-双(2-吡啶乙基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及性质

Two Trinuclear copper(Ⅱ) complexes bridged with N,N′-Bis(2-pyridylethyl)-Dithiooxamidate, [Cu₃L₂](ClO₄)₂ (1) and [Cu₃L₂](NO₃)₂ (2) (H₂L=N,N′-Bis(2-pyridylethyl)-Dithiooxamide), have been synthesized, and characterized by elemental analyses, IR, UV-Visible spectra, conductance and EPR spectra. The variable temperature magnetic susceptibility for complex 1 has been measured in the temperature range of 1.5～298 K. Experimental data of magnetic susceptibility are successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=S₃=1/2, giving the magnetic exchange parameters of 2J=-221.6 cm^-1 and 2j=-15.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Cu(Ⅱ) ions.     

二代树状碳硅烷液晶研究——端基含36个己氧基偶氮苯介晶基元

用发散法合成周边含36个己氧基偶氮苯介晶基元(M3)端基的新的二代树状碳硅烷液晶(D2),并用元素分析、氢谱、激光质谱、红外光谱、紫外-可见光谱、偏光显微镜,DSC和WAXD法进行表征.D2为向列相,与M3相同.D2液晶态相行为是K90N105I1l3N75K,D2熔点比M3降低2633℃,D2清亮点比M3降低315℃,D2液晶态温区比M3加宽1130℃.D2和一代树状物D1的相态由介晶基元相态决定.D2熔点比D1降低23℃.D2清亮点比D1降低1121℃,D2液晶态温区比D1减少819℃.     

铜配位聚合物[Cu(C5H6S5)(SCN)]∞的合成和结构研究(英)

The Copper(Ⅰ) supramolecular complexes of 4,5-bis(methylthio)-1,3-dithiole-2-thione (C₅H₆S₅), [Cu(C₅H₆S₅)(SCN)]_∞ 1 and [Cu(C₅H₆S₅)I]_∞ 2, have been prepared and characterized. X-ray structure analysis for complex 1 reveals that the infinite chain structure with polymeric stairs of different lengths is formed through the coordination mode (μ₃) of the thiocyanate bridges. The shorter interchain S…S contacts give rise to a three-dimensional network structure. CCDC: 215668.     

三齿多吡啶钴(II)配合物的合成、表征及其与DNA的相互作用研究

合成了两种三齿多吡啶钴(II)配合物 (A)和[Co(H₂Bzimpy)₂]Cl₂ (B), 用元素分析、IR对配合物的组成和结构进行了表征, 测定了配合物A的晶体结构. 用电子吸收光谱、荧光光谱、循环伏安法及凝胶电泳实验等方法研究了配合物与DNA的相互作用. 结果表明配合物A和B与小牛胸腺(CTDNA)的作用属部分插入和静电结合, 凝胶电泳实验表明配合物A在310 nm光辐射15 min, 可使超螺旋pBR322DNA断裂为开环缺口型和线型DNA.     

手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应

合成了三种新的含C₂-对称轴的手性胺醇(PhOHCHCH₂)₂NCH₂C₆H₄R (R＝OCH₃, L₁; R＝CH₃, L₂; R＝Cl, L₃), 将其与无水氯化稀土LnCl₃•4THF (Ln＝La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L＝L₁, L₂, L₃; Ln＝La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L₁/SmCl₃•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%.     

二硫代草酸根桥联的双核镍(Ⅱ)配合物研究

Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni₂(Bpy)₃(Dto)₂(H₂O)₃(1), Ni₂(Phen)₃(Dto)₂(H₂O)₃(2) and Ni₂(Me₂Bpy)₃(Dto)₂(H₂O)₂ (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me₂Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto^2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=1, giving the magnetic exchange parameters of 2J=-52.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.     

2-氨基-4-噻唑乙酸乙酯构筑的两个镉配合物的晶体结构及荧光性质

以2-氨基-4-噻唑乙酸乙酯(EATA)和氯化镉水合物为原料,在无水乙醇和乙醇-水混合物两种溶剂中分别合成了配合物[CdCl₂(EATA)]_n(1)和[CdCl₂(EATA)₂](2),并利用X-射线单晶衍射、元素分析、红外光谱和荧光光谱对它们进行了表征。配合物1和2都属于单斜晶系,分别为P2₁/c和Cc空间群,它们的中心金属离子Cd²⁺均为扭曲的六配位八面体构型。在配合物1中,相邻的2个八面体单元通过2个μ₂-Cl-阴离子双桥连形成一维链结构,该一维链进一步通过N-H…Cl分子间氢键形成了三维网络结构,而配合物2则通过大量的N-H…Cl和C-H…Cl分子间氢键等弱作用组装成二维超分子结构。固态荧光光谱分析表明,配合物1和2荧光性质相似,均可归属于由配体到金属间的电荷转移(LMCT)。     

A Novel Pentaerythritol-based Carbosilane Liquid Crystalline Dendrimer Containing 12 Nitroazobenzene Groups on the Periphery

A novel liquid crystalline dendrimer with peripheral mesogenic units was successfully prepared. Azo-reaction and Williamson synthesis were employed in the preparation of the mesogenic unit 4-[4-(6-hydroxyhexyloxy)-phenylazo]nitrobenzene (M-NO2). A terminal Si-Cl functional carbosilane dendrimer based on pentaerythritol was used as dendritic scaffold and subsequently functionalized with the aforementioned groups. Investigation of the liquid crystalline properties of the mesogen-functionalized dendrimer PCSi-IG-NO2 by polarizing optical microscopy, DSC, and X-ray diffraction showed that it exhibits smectic E (SE) phase, different from the corresponding mesogenic unit, which shows nematic phase. Furthermore, the temperatures of both the melting point and the clearing point of the mesogen-functionalized dendrimer decrease, and the temperature region of the SE phase is wider than that of the nematic phase.     

三代碳硅烷光致变色液晶树状物的光化学研究——端基含108个4-丁氧基偶氮苯介晶基元

报道了新化合物含108个丁氧基偶氮基元端基的三代(D3)碳硅烷光致变色液晶树状物在各溶液中的反-顺光异构化(光致变色)反应速率常数k_p, 光化学回复异构化正/逆反应速率常数k_t和k_c, 热回复异构化反应速率常数k_H, 光化学回复异构化反应平衡常数k_t/k_c, 活化能E, 异构化转换率及热回复异构化反应中的反-顺异构体组分比. D3的光致变色反应速率常数为10^－1 s^－1, 而含偶氮基元的光致变色液晶聚硅氧烷的光致变色反应速率常数为10^－8 s^－1, 因此, D3的光响应速度比后者快10⁷倍.     

Liquid-crystalline carbosilane dendrimers of different molecular architecture with photochromic mesogenic and aliphatic terminal groups

Second-generation (G-2) liquid-crystalline carbosilane block and statistical dendrimers with aliphatic (decyl) and photochromic (azobenzene-containing) mesogenic terminal groups and a G-2 homo-dendrimer containing the same mesogenic terminal groups were synthesized for the first time. The influence of dendritic architecture on the phase behavior of the dendrimers and on photoinduced Z-E-isomerization of the azobenzene fragments in mesogenic terminal groups in dendrimer solutions are discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2325–2331, December, 2007.     

外围含对-硝基偶氮苯介晶基团的椭球型硅碳烷树状物

Novel carbosilane liquid crystalline dendrimers based on 1,6-hexanediol were prepared. Using the precursors Gn-C1 （n = 1-3） with Si-C1 bonds on the periphery as dendritic scaffolds and 4-[4-（6-hydroxyhexyloxy）phenylazo]- nitrobenzene as mesogenic group, a series of carbosilane liquid crystalline dendrimers from the first to the third generation were synthesized. These carbosilane liquid crystalline dendrimers showed smectic phase.     

Liquid crystalline dendrimer of the fifth generation: From lamellar to columnar structure in thermotropic mesophases

The structure of a liquid crystalline (LC) carbosilane dendrimer of the fifth generation bearing 128 terminal cyanobiphenyl mesogenic groups has been studied. This dendrimer was synthesized by a hydrosilylation reaction and then the cyanobiphenyl mesogenic groups were chemically linked to the dendritic matrix via a-OOC-(CH2)10-Si(CH3)2OSi(CH3)2-spacer. Structural studies carried out by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction methods revealed unusual phase behaviour. At room temperature the dendrimer forms a lamellar (smectic A) phase which develops in-plane ordering above 40C.This is due toa tendency to form columns ofmolecules which areprobably perpendicular to the layers. Above 121C the material transforms into another more disordered mesophase which is probably a disordered hexagonal columnar phase. The proposed structures and molecular packing in these different types of mesophase are discussed.     

二代树状碳硅烷液晶研究I.端基含36个丁氧基偶氮苯介晶基元

用发散法合成周边含36个丁氧基偶氮苯介晶基元（M5）端基新的二代树状碳硅 烷液晶（D_2），并用元素分析，氢谱，激光质谱，红外，紫外，偏光显微镜，DSC和WAXD法表 征D2为向列相，与M5相同，二代树状物相态由介晶基定．D2液晶态相行为是 K85N107I103N69K，其熔点比M5降低27-41℃，清亮点比M5降低17-18宽10-23℃．二 代碳硅烷（D2）与一代碳硅烷（D1）相比熔点增加2-3℃，清亮点降低26-29℃，液 晶态温区减少℃．在二代树状物中观察到S＝＋3／2的高强向错．     

偶氮型光致变色液晶树状大分子的量子产率、异构转化率和活化能研究

研究了化合物端基含36个己氧基偶氮苯介晶基元的二代(G2)光致变色液晶树状大分子在氯仿及四氢呋喃溶液中的量子产率、吸收光强Ia、活化能E、异构转化率A/A0、热回复异构化速率常数kH及其反/顺异构体组分比A′/A′0,并与一代光致变色液晶碳硅烷树状大分子(G1)及介晶基元化合物(M3)的光化学行为进行了比较.在氯仿及四氢呋喃溶液中的量子产率的顺序均为M3>G1>G2,吸收光强Ia在氯仿及四氢呋喃溶液中的顺序分别为G2>G1>M3(氯仿)和M3>G1>G2(四氢呋喃),在氯仿及四氢呋喃溶液中活化能的顺序均为M3>G2>G1,在氯仿及四氢呋喃溶液中热回复异构化速率常数kH的顺序均为G1>G2>M3,在热回复异构化反应中的反/顺异构体组分比A′/A0′在氯仿及四氢呋喃溶液中的顺序均为G2>G1>M3.     

端基含108个己氧基偶氮苯介晶基元三代树状碳硅烷液晶研究

用发散法合成以四碳硅烷为核心,周边含108个己氧基偶氮苯介晶基元(M3)端基的三代树状碳硅烷(D3)液晶,并用元素分析、核磁共振、激光解吸电离飞行时间质谱、红外光谱、紫外光谱、偏光显微镜、差示扫描量热(DSC)和X射线衍射法(WAXD)进行表征.D3为向列相液晶,与M3相同,三代(D3)、二代(D2)和一代(D1)树状物的相态由介晶基元的相态决定.D3的液晶态相行为是K79N136I132N,D3的熔点比M3的低19℃,D3的清亮点比M3的增加16℃,D3液晶态温区比M3宽35℃.     

二代光致变色液晶树枝状碳硅烷的光化学研究——端基含36个丁氧基偶氮苯介晶基元

研究了新的含36个丁氧基偶氮苯介晶基元的二代光致变色液晶树枝状碳硅烷(D2)在氯仿、四氢呋喃溶液中的光强,吸收光强,摩尔消光系数,最大吸收波长,量子产率,活化能,异构转换率,光回复异构化反应平衡常数,反-顺光异构化反应速率常数,光回复异构化正/逆和热回复异构化反应速率常数.