二维镍配位聚合物(Ni-CP)和Ag@Ni-CP肖特基结的制备及其光催化降解阳离子染料

采用水热法合成了一种新的二维镍(Ⅱ)配位聚合物(Ni-CP),命名为[Ni(DDB)_0.5(2,2′-bipy)(H₂O)]·H₂O(H₄DDB=1,4-二(3,5-二羰基苯氧基)苯,2,2′-bipy=2,2′-联吡啶),并通过元素分析、热重分析、粉末X射线衍射、扫描电镜、透射电镜和X射线光电子能谱对其进行了表征。单晶结构分析表明,配位聚合物通过DDB^4-配体以μ₄方式形成二维波浪状网络结构。采用光还原法制备了具有肖特基结的Ag负载产品(Ag@Ni-CP)。研究了Ni-CP和Ag@Ni-CP的光催化降解性能,后者表现出优异的降解效果,特别是对罗丹明B和亚甲蓝,60 min内降解率快速高达99%,与报道的金属有机骨架催化剂材料相比,Ag@Ni-CP表现出更高更快的降解性能。通过自由基俘获实验研究了Ag@Ni-CP的光催化机理。     

一例由BMIP和1,4-BDF混合配体构筑的Zn(Ⅱ)配位聚合物、晶体结构及其性能

以1,3-双(2-甲基-1H-咪唑-1-基)丙烷(BMIP)、2,3,5,6-四氟对苯二甲酸(1,4-BDF)和Zn(NO₃)₂·6H₂O为原料,在溶剂热条件下合成了一例结构新颖的Zn(Ⅱ)配位聚合物:{[Zn(1,4-BDF)(BMIP)·H₂O]}_n,并用元素分析(EA)、热重分析(TGA)、红外光谱(FT-IR)和X-射线单晶衍射等手段对配位聚合物进行了表征。X-射线单晶衍射结果表明,配位聚合物具有独特的1维环状锯齿链结构。光催化降解实验表明,配位聚合物对罗丹明B(Rh B)和亚甲基蓝(MB)表现出良好的光催化降解性能,降解效率分别为79.7%和93.9%。此外,固体荧光测试结果表明,配位聚合物具有较强的荧光发射性质并且对苯胺(Aniline)和硝基苯(NB)具有良好的荧光传感性能,最低检测限分别为5.58×10^-3 mol/L和5.43×10^-3 mol/L。     

基于Keggin型杂多酸的无机-有机杂化物的合成和光催化活性

采用水热合成方法制备了2个基于Keggin型杂多酸的无机-有机杂化物, 化学式分别为{[Cu₂(4,4′- bipy)₄(H₂O)₄](SiMo₁₂O₄₀)·18H₂O}_n(1)和{[Cu₂(4,4′-bipy)₄(H₂O)₄](PMo₆W₆O₄₀)·18H₂O}_n(2)(bipy=bipyridine). 结构分析 表明2个化合物同构, Cu²⁺是六配位, 分别与4个4,4′-bipy上的N原子和2个水分子上的O原子结合, 形成 [Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺二维层状结构. 杂多阴离子通过静电与配位阳离子[Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺作用交叉排列在层间. 通过红外光谱、 粉末X射线衍射和固体紫外-可见漫反射光谱等对化合物的性质进行了表征. 研究了所合成化合物对水溶性染料亚甲基蓝的降解活性, 发现2种化合物对于亚甲基蓝均表现出显著的光降解活性, 并对它们的催化机理进行了讨论.     

新型含氮配体钴配合物的水热合成、晶体结构及荧光性质

以4,5-二羟基苯-1,3-二磺酸钠（Na₂H₂L）和4,4′-bipy为原料,采用水热法与Co(NO₃)₂反应合成了新的含氮配体钴配合物[Co(4,4′-bipy)(H₂O)₄]·H₂L·2H₂O（1）（H₂L^2-=4,5-二羟基苯-1,3-二磺酸根离子,4,4′-bipy=4,4′-联吡啶）,其结构和组成经X-射线单晶衍射、红外光谱、元素分析和热重分析表征。晶体结构解析表明：钴离子与4,4′-bipy和水分子配位,形成扭曲的八面体配位构型。H₂L^2-配体没有配位,仅起平衡电荷作用。在结构单元中,[Co(4,4′-bipy)(H₂O)₄]²⁺, H₂L^2-和自由水分子之间通过氢键相连。配合物的荧光发射峰与配体相比发生了蓝移,最大发射峰位于357 nm。     

刚性4-取代双三唑配体构筑的三个锌配合物的合成和荧光

在室温下合成了3个新的配位聚合物{[Zn(4?Nbdc)(btx)]·2H₂O}_n(1·2H₂O)、[Zn(btx)_1.5(1,3?bdac)]n(2)和{[Zn(mbtx)(1,3?bdc)(H₂O)₂]·H₂O}_n(3)(btx=1,4?二(4H?1,2,4?三唑)苯,mbtx=1,3?二(4H?1,2,4?三唑)苯,4?Nbdc=4?硝基邻苯二甲酸根,1,3?bdac=间苯二乙酸根,1,3?bdc=间苯二甲酸根),测试了配合物的单晶结构,并从元素分析、红外和粉末衍射等方面进行表征。单晶X射线衍射表明,配合物1是二维(4,4)网格结构,配合物2和3都是一维链状结构。配合物2中的π?π作用将一维链连接成三维网格结构。在配合物3中,分子间氢键将一维链连接成二维网格,2套二维网格在分子间氢键的作用下相互穿插得到2D+2D→2D的网格结构。同时,还研究了3个配位聚合物的荧光和热稳定性。     

2种同构紫精配位聚合物的合成及其光致变色性能

变色材料作为一种新型的智能材料,在光存储信息和光学器件等领域具有巨大的应用潜力。以具有柔性骨架的紫精配体1,1’-双(4-羧基苄基)-4,4’-联吡啶二氯化物(H₂BpybcCl₂)作为功能配体,与过渡金属离子Mn²⁺和Cd²⁺自组装,合成2个同构配位聚合物[Mn(Bpybc)Cl₂·H₂O]_n(1)和[Cd(Bpybc)Cl₂·4H₂O]_n(2)。X射线单晶衍射表明,2个化合物为一维链状结构。在紫外灯照射下,光诱导电子转移而产生紫精自由基,2种化合物均表现出明显的光致变色行为。     

三氮唑取代杯[4]芳烃配位聚合物的合成与荧光性能

利用四[1-(1, 2, 4-三氮唑基)甲基]间苯二酚杯[4]芳烃配体(TTR4A)在溶剂热的条件下合成了两个配位聚合物,[[Zn₂(TTR4A)(L)₂]·DMF·4H₂O]_n(化合物1) (DMF = N, N-二甲基甲酰胺)和[[Co(TTR4A)Cl₂]·DMA·H₂O]_n (化合物2) (H₂L = 4, 4’-联苯二甲酸) (DMA = N, N-二甲基乙酰胺)。通过单晶X射线衍射方法对这两个配位聚合物的结构进行了确定。利用红外、元素分析、粉末X射线衍射(PXRD)和热重表征手段对化合物1和2进行了表征。在化合物1中,四个L配体连接着四个Zn(Ⅱ)离子形成了环状的Zn₄L₄结构单元,该结构单元进一步地被TTR4A链接形成了一维链状结构。在化合物2中,TTR4A的四个三氮唑基团各连接一个Co(Ⅱ)离子形成二维层状结构。此外,我们对化合物1的荧光性能进行了研究,荧光测定表明固态条件下化合物1发出很强的荧光,并能够选择性地对Fe³⁺、Cr₂O₇²⁻和硝基苯分子产生响应。     

一个基于[Cu4(μ2-OH)2N12]的10-连接3D配合物的合成、结构和光催化性质

通过扩散法合成了一个新的配位聚合物{[Cu₂（OH）（btre）_1.5（1,2,4-btc）]·13H₂O}_n（1·13H₂O）（btre=1,2-二（4H-1,2,4-三唑）乙烷,1,2,4-btc=1,2,4-苯三甲酸根）。测试了1·13H₂O的晶体结构,并用红外光谱、元素分析、粉末X射线衍射对其进行表征。单晶X射线衍射表明1是基于四核铜簇[Cu₄（μ₂-OH）₂N₁₂]构筑的10-连接的3D框架,其拓扑符号为3¹²·4²⁸·5⁵。研究了1·13H₂O的热稳定性以及对甲基橙的催化降解作用。     

羧苄基紫精配位聚合物的多重响应行为

随着智能材料的不断发展,多重刺激响应型紫精配位聚合物有望应用于材料学和生物学等工程领域,引起了广泛的兴趣。为了获得此类化合物,以羧苄基紫精、1,1’-双(4-羧苄基)-4,4’-联吡啶二氯化物(H₂BpybcCl₂)为功能配体,与过渡金属离子Ni²⁺(1)、Mn²⁺(2)和Co²⁺(3)自组装反应,形成3个相同结构的二维配位聚合物{[M₂(Bpybc)₃(H₂O)₆]·(OH)₄·nH₂O}_n。由于紫精自由基的存在,在紫外灯照射下,3个化合物均表现出明显的光致变色行为。加热的条件下,3个化合物也表现出由于脱水导致的配位场d-d跃迁而发生的颜色变化。     

基于V型双咪唑与二羧酸混合配体Zn2+配位聚合物的合成、结构与性质

通过溶剂热合法,制备了两种新的Zn²⁺配位聚合物{[Zn(bib)(bdc)]•DMF}_n(1)和{[Zn(bib)(bpdc)]•H₂O}_n(2)(bib=1,3-双(1-咪唑)苯,H₂bdc=1,4-苯二甲酸,H₂bpdc=4,4'-联苯二甲酸,DMF=N,N-二甲基甲酰胺）。通过单晶X-射线衍射确定了两个配合物的结构：配合物1属于三斜晶系,空间群为P-1,是一种由bib和ndc^2-配体混合连接二维网络结构,配合物2属于单斜晶系,空间群为P2₁/n,表现出了二重互穿二维网络结构。      

Synthesis and structure of hydroxyisoxazolidines and derivatives of hydroxylamine and alkenals

The reactions of N-substituted hydroxylamines with alkenals serve as a method for the synthesis of the corresponding 2-substituted 3(5)-hydroxyisoxazolidines. The reaction pathway is determined by the nature of the substituent attached to the nitrogen atom. Ring-chain isomerism has been detected in these newly obtained compoundsTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1276, September, 1987.     

Mass and NMR spectra of haplophyllidine and perforine and of their derivatives

Conclusions The mass and NMR spectra of haplophyllidine, perforine, and their derivatives have been studied. The influence of the open and cyclic forms of the molecular ion on the nature of the fragmentation has been discussed. The main routes of fragmentation of the compounds considered are due to the presence of substituents at C₈ and C₄.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 273–279, 1969     

Crystal and molecular structure of aroyl- and acetylhydrazones of acet- and benzaldehydes

Aroyl- and acetylhydrazones of acet- (I) and benzaldehydes (IV) and benzoylhydrazones of acet- (II) and benzaldehydes (III) were studied by x-ray structural and quantum-chemical methods in order to establish their structures. Compund (I) was the EEZ structure in the crystal. Calculations and spectral data showed that the EEE form occurs in nonpolar solvents and in the gas phase. According to crystallographic data molecules (I)–(IV) are the E-isomers (relative to the N-N bond) and the hydrazone fragments are planar. Intermolecular N-H...O H-bonds from in the crystals. The data obtained suggest that the majority of acylhydrazones are conformationally rigid on dissolution although exceptions do occur. Apparently the reasons for the difference of acetyl- and benzoylhydrazones in electrocarboxylation reactions are electronic and not steric factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 75–81, January, 1991.     

Investigation of adhesion and mobility of polyurethane and epoxy-rubber glues and adhesives

The values of activation parameters in uncured and cured epoxy resins, rubbers, and blends thereof are investigated. The dependences of activation energy and adhesion strength of epoxy-rubber compositions on rubber content are determined. The correlation of adhesion and activation energy values for polyurethane rubber and epoxy-rubber compositions is shown.     

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.     

Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium

Reaction of the proligand Ph2PN(SiMe3)2 (L1) with WCl6 gives the oligomeric phosphazene complex [WCl4(NPPh2)]n, 1 and subsequent reaction with PMe2Ph or NBu4Cl gives [WCl4(NPPh2)(PMe2Ph)] (2) or [WCl5(NPPh2)][NBu4] (3), respectively. DF calculations on [WCl5(NPPh2)][NBu4] show a W=N double bond (1.756 A) and a P-N bond distance of 1.701 A, which combined with the geometry about the P atom suggests, there is no P-N multiple bonding. Reaction of L1 with [ReOX3(PPh3)2] in MeCN (X = Cl or Br) gives [ReX2(NC(CH3)P(O)Ph2)(MeCN)(PPh3)](X = Cl, 4, X = Br, 5) which contains the new phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6 degrees, when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2(L2H) reacts with [(C5H5)TiCl3] to give [(C5H5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen atoms. Reaction of the proligands Ph2PNHNR2[R2 = Me2 (L2H), -(CH2CH2)2NCH3 (L3H), (CH2CH2)2CH2 (L4H)] with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave [RuCl2(eta6-p-MeC6H4iPr)L] {L = L2H (7), L3H (8), L4H (9)}. The X-ray crystal structures of 7-9 confirmed that the phosphinohydrazine ligand is neutral and bound via the phosphorus only. Reaction of complexes 7-9 with AgBF4 resulted in chloride ion abstraction and the formation of the cationic species [RuCl(6-p-MeC6H4iPr)(L)]+ BF4- {(L = L2H (10), L3H (11), L4H (12)}. Finally, reaction of complex 6 with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave the binuclear species [(eta6-p-MeC6H4iPr)Cl2Ru(mu2,eta3-Ph2PNNMe2)TiCl2(C5H5)], 13.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。