三水合希土氯化物（镨、钆）与18－冠－6配合物的热化学研究

制备了ＲＥＣｌ３·３Ｈ２Ｏ（ＲＥ＝Ｐｒ、Ｇｄ）与１８Ｃ６的固态配合物，其化学组成为：ＲＥＣｌ３·１８Ｃ６·３Ｈ２Ｏ．对其进行了ＩＲ、溶解度、ＤＴＧ和ＴＧ分析．推测了热分解机理．测量了２９８．１５Ｋ时１８Ｃ６及两种配合物在无水乙醇中的积分溶解热，以及ＲＥＣｌ３·３Ｈ２Ｏ在１８Ｃ６－Ｃ２Ｈ５ＯＨ溶液中的溶解配位热效应．依据本文所设计的热化学循环，求得了ＲＥＣｌ３·３Ｈ２Ｏ（ｓ）与１８Ｃ６（Ｓ）生成ＲＥＣｌ３·１８Ｃ６·３Ｈ２Ｏ（Ｓ）的反应热及两种配合物的标准生成焓．     

三水合希土氯化物(镨、钆)与18－冠－6配合物的热化学研究

制备了ＲＥＣｌ３．３Ｈ２Ｏ（ＲＥ＝Ｐｒ，Ｇｄ）与１８Ｃ６的固态配合物，其化学组成为：ＲＥＣｌ３，１８Ｃ６．３Ｈ２Ｏ。对其进行了ＩＲ，溶解度、ＤＴＧ和ＴＧ分析，推测了热分解机理，测量了２９８．１５Ｋ时１８Ｃ６及两种配合物在无水乙醇中的积分，及ＲＥＣｌ３，３Ｈ２Ｏ在１８Ｃ６－Ｃ２Ｈ２ＯＨ溶液中的溶解配位热效应，依据本文所设计的热化学循环，求得了ＲＥＣｌ３，３Ｈ２Ｏ（ｓ）与１８Ｃ６（ｓ）生成ＲＥＣｌ３，     

稀土与α—萘乙酸配合物的合成和性质研究

本文合成了１１种稀土与α－萘乙酸的配合物。元素分析结果表明配合物的组成为ＲＥ（Ｃ１２Ｈ９Ｏ２）３．２Ｈ２Ｏ（ＲＥ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｅｒ，Ｙｂ，Ｙ），并通过配合物的ＩＲ，ＵＶ，Ｈ－ＮＭＲ，ＴＧ－ＤＴＡ，ＸＰＳ，磁化率，摩尔电导及溶解性的研究。     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成,表征以…

合成了通式为Ｋ１５Ｈ３〔Ｃｅ（Ｐ２Ｗ１６ＶＯ６１）２〕．６１Ｈ２Ｏ、Ｋ１５Ｈ４〔Ｌｎ（Ｐ２Ｗ１６ＶＯ６１）２〕．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋，Ｐｒ＾３＋，Ｎｄ＾３＋，Ｓｍ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋）的９种镧系元素Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物，并用ＩＲ、ＵＶ、ＮＭＲ、ＥＳＲ、ＸＲＤ、ＴＧ－ＤＴＡ等对其结构和性质进行子研究。该类配合物具有与Ｋ１６〔Ｃｅ（Ｐ２Ｗ１７Ｏ     

RE（NO3）3与丝氨酸间配合行为的半微量相平衡研究

测定了ＲＥ（ＮＯ３）３－Ｓｅｒ－Ｈ２Ｏ（ＲＥ＝Ｓｍ，Ｇｄ，Ｙｂ）三元体系在２５℃的溶度和饱和溶液折光率，各体系的溶度曲线和饱和溶液折光曲线均由四支组成，分别与ＲＥ（ＮＯ３）３．ｎＨ２Ｏ（ＲＥ＝Ｓｍ，Ｇｄ，ｎ＝６；ＲＥ＝Ｙｂ，ｎ＝５）配合物ＲＥ（Ｓｅｒｉｍｅ）（ＮＯ３）３．４Ｈ２Ｏ（一致溶解化合物），ＲＥ（Ｓｅｒｉｎｅ）４（ＮＯ３）３．６Ｈ２Ｏ（不一致溶解化合物）和Ｓｅｒｉｎｅ相对应。     

三水合氯化镨与18C6在乙醇中的配位行为及配合物的合…

采用半微量相平衡方法研究了ＰｒＣｌ３．３Ｈ２Ｏ－１８Ｃ－Ｃ２Ｈ５ＯＨ三元体系在２５℃的溶解度，测定了各饱和溶液的折光率，在该体系中有三种化学计量的配合物形成，其化学组成为：２ＰｒＣｌ３．１８Ｃ６．６Ｈ２Ｏ．Ｃ２Ｈ６ＯＨ，４ＰｒＣｌ３．３（１８Ｃ６）．１２Ｈ２Ｏ和ＰｒＣｌ３．１８Ｃ６．３Ｈ２Ｏ依据相平衡结果，合成了三咱固态配合物，利用化学分析、ＩＲ、ＴＧ、ＤＴＧ、ＤＳ电导研究了配合物的组成和性质。     

Y（ClO_4）_3·3H_2O－B15C5－CH_3CN三元体系在20℃时的半

采用半微量相平衡方法研究了Ｙ（ＣｌＯ_４）_３·３Ｈ_２Ｏ－Ｂｌ５Ｃ５－ＣＨ_３ＣＮ三元体系在２０℃时的溶解度，测定了各饱和溶液的折光率．该体系于２０℃生成两种化学计量的配合物，其组成分别为Ｙ（ＣｌＯ_４）_３·Ｂ１５Ｃ５·３Ｈ_２Ｏ·２．５ＣＨ_３ＣＮ和Ｙ（ＣｌＯ_４）_３·２Ｂ１５Ｃ５·３Ｈ_２Ｏ·ＣＨ_３ＣＮ。用ＩＲ光谱、电导、ＤＴＧ、ＴＧ和ＤＳＣ研究了配合物的组成和性质。     

取代型钨镓杂多配合物的导电性及其磁性

合成了过渡金属取代的钨镓杂多配合物α－Ｎａ７「ＧａＷ１１Ｃｏ（Ｈ２Ｏ）Ｏ３９」．１６Ｈ２Ｏ，α－Ｎａ７Ｈ２「ＧａＷ１０Ｃｏ２（Ｈ２Ｏ）２Ｏ３９」．１６Ｈ２Ｏ和α－ＮａｎＨｍ「ＧａＷ９ＭＥ（Ｈ２Ｏ）３Ｏ３７」．１６Ｈ２Ｏ「Ｍ＝Ｃｏ（Ⅱ），Ｎｉ（Ⅱ，）Ｖ（Ⅴ）」，通过红外，紫外，ＩＣＰ，ＴＧ－ＤＴＡ，ＥＰＲ，ＸＰＳ，＾１８３ＷＮＭＲ，极谱等手段进行了表征。     

Gd（ClO_4）_3·3H_2O－18C6－CH_3CN三元体系25℃相平衡研究及配合物的合成与表征

采用半微量相平衡方法研究了Ｇｄ（ＣｌＯ_４）_３·３Ｈ_２Ｏ－１８Ｃ６－ＣＨ_３ＣＮ三元体系在２５℃时的溶解度，测定了饱和溶液的折光率。结果表明，该体系在２５℃时形成两种化学计量的配合物，其组成分别为：Ｇｄ（ＣｌＯ_４）_３·１８Ｃ６·３Ｈ_２Ｏ·２ＣＨ_３ＣＮ和Ｇｄ（ＣｌＯ_４）_３·２（１８Ｃ６）·３Ｈ_２Ｏ·２ＣＨ_３ＣＮ，制备了固态配合物，用化学分析及元素分析、ＩＲ、ＤＴＧ、ＴＧ及ＤＳＣ等研究了配合物的组成与性质。     

希土脯氨酸邻菲 啉固体配合物合成和表征

本文报道首次合成了希土离子ＲＥ３＋ （ＲＥ＝ Ｙ、Ｌａ、Ｎｄ、Ｓｍ 、Ｅｕ、Ｅｒ）与脯氨酸（Ｐｒｏ）、邻菲?啉（Ｐｈｅｎ）形成的三元固体配合物,对它们进行了元素分析,确定其化学组成为［ＲＥ（Ｐｒｏ）３ｐｈｅｎ］Ｃｌ３·２Ｈ２Ｏ,用摩尔电导、ＩＲ·Ｆａｒ－ＩＲ、ＵＶ、ＸＰＳ、１Ｈ ＮＭＲ、ＴＧ－ＤＴＡ 分析等研究了配合物的有关性质。     

New layered rare-earth hydroxides with anion-exchange properties

We report the synthesis of a new series of layered hydroxides based on rare-earth elements with a composition of RE(OH)2.5Cl(0.5).0.8 H2O (RE: Eu, Tb, etc.) through the homogeneous precipitation of RECl3.x H2O with hexamethylenetetramine (HMT). Rietveld analysis combined with direct methods revealed an orthorhombic layered structure comprising a positively charged layer of [RE(OH)2.5-(H2O)0.8]0.5+ and interlayer Cl- ions. The Cl- ions were readily exchangeable for various anions (NO3-, SO4(2-), dodecylsulfonate, etc.) at ambient temperature. Photoluminescence studies showed that the compounds display typical RE3+ emission. With rare-earth-based host layers and tunable interlayer guests, the new compounds may be of interest for optoelectronic, magnetic, catalytic, and biomedical materials.     

钌分子氢配合物催化烯烃的离子氢化

在氢气压力下，钌配合物[^MeCnRuCl(dppe)](O3SCF3)与AgO3SC3在CH2Cl2中反应生成分子氢配合物[^MeCnRu(H2)(dppe)](O3SCF3)2，该分子氢配合物具有催化烯烃离子氢化的活性。原位高压核磁共振研究显示，这种催化离子氢化反应可能是由分子氢配合物向烯烃转移氢质子形成碳正离子引起的。     

Thermally stable luminescent composites fabricated by confining rare earth complexes in the two-dimensional gallery of titania nanosheets and their photophysical properties

Fluorescent composite materials of exfoliated titania nanosheets, Ti(0.91)O(2), and rare earth (RE) complexes, Eu(phen)(2)Cl(3).2H(2)O and Tb(phen)(2)Cl(3).2H(2)O (phen = 1,10-phenanthroline), were synthesized via flocculation between them. X-ray diffraction measurements and transmission electron microscopy observations confirmed a restacked lamellar structure for the composites, and elemental analysis revealed a high RE complex content of 15 wt %. The decomposition temperature of the complexes trapped in the composites was improved to 420 degrees C from 250 degrees C for the free form. The restacked composite composed of Ti(0.91)O(2) nanosheets and Eu(phen)(2) exhibited characteristic red emission from the complex, while the composite with Tb(phen)(2) gave featureless emission originated from the ligand. This phenomenon can be explained by a shift of triplet state level of the ligand after encapsulation in the host titania nanosheets. The quantum yield of europium complex in the composite was enhanced 1.6 times more than that of the pure complex.     

Isomeric effects in the gas-phase reactions of dichloroethene, C2H2CL2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH(4)(+), H(3)O(+), SF(3)(+), CF(3)(+), CF(+), SF(5)(+), SF(2)(+), SF(+), CF(2)(+), SF(4)(+), O(2)(+), Xe(+), N(2)O(+), CO(2)(+), Kr(+), CO(+), N(+), N(2)(+), Ar(+), F(+), and Ne(+)) with the three structural isomers of dichloroethene, i.e., 1,1-C(2)H(2)Cl(2), cis-1,2-C(2)H(2)Cl(2), and trans-1,2-C(2)H(2)Cl(2) is reported. The recombination energy (RE) of these ions spans the range of 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube (SIFT). Collisional rate coefficients are calculated by modified average dipole orientation (MADO) theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C(2)H(2)Cl(2) with photon energies in the range of 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H(3)O(+), CF(3)(+), and CF(+). For 1,1-C(2)H(2)Cl(2) the reaction with H(3)O(+) proceeds at the collisional rate with the only ionic product being 1,1-C(2)H(2)Cl(2)H(+). However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C(2)H(2)Cl(2), but only proceeds with 14% and 18% efficiency, respectively. The CF(3)(+) reaction proceeds with 56-80% efficiency, the only ionic product for 1,1-C(2)H(2)Cl(2) being C(2)H(2)Cl(+) formed via Cl(-) abstraction, whereas the only ionic product for both 1,2-isomers is CHCl(2)(+) corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C(2)H(2)Cl(2) isomers, have been found in the reactions of SF(+), CO(2)(+), CO(+), N(2)(+), and Ar(+). Although these five ions have REs above the ionization energy (IE) of any of the C(2)H(2)Cl(2) isomers, and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C(2)H(2)Cl(2) is responsible for the observed effects.     

Keggin结构阳离子[AlO4Al12(OH)24(H2O)12]7+与杂多阴离子构筑的新型无机纳米簇凝胶

多金属氧酸盐（Polyoxometalates POMs）化学已成为材料科学、医学、催化及光化学等诸多领域的活跃研究课题[1～5]。     

钐、铕-2,4-二氯苯氧乙酸的二元、三元配合物的合成及荧光性能

以2,4-二氯苯氧乙酸为第一配体、1,10-菲罗啉为第二配体,合成了钐、铕的二元、三元配合物。通过元素分析、EDTA络合滴定及热重分析,确定了配合物的通式为RE(DCP)3.H2O,RE(DCP)3phen(RE=Sm,Eu;DCP=2,4-二氯苯氧乙酸根;phen=邻菲罗啉);测定了配合物红外光谱、紫外光谱、荧光光谱;研究了配合物的热稳定性。结果表明,三元配合物较二元配合物稳定;Eu(DCP)3.H2O和Eu(DCP)3phen具有荧光性能。     

Synthesis and Determination of Standard Molar Enthalpies of Formation for Complexes of Rare Earth Isothiocyanates with Glycine

Four solid complexes of rare earth isothiocyanates with glycine were synthesized. They were characterized by chemical analysis, elemental analysis, Infrared spectra, X-ray powder diffraction and TO-DSC analysis. Their chemical formulae were proved to be RE(NCS)2.Gly .H2O, where RE is La, Ce, Pr or Nd. The integral heats of solution of RE(NCS)3.3Gly. H2O in water, of RE(NCS)2. 7H2O in aqueous glycine solution and of glycine in water have been measured calorimetricaliy at 298. 15K. By means of a thermochemical cycle suggested in this paper, the standard molar enthalpies of formation for RE(NCS)2. 3Gly.H2O(c) were obtained and their lattice energies were calculated.     

Rare-Earth–Transition-Metal Organic–Inorganic Hybrids Based on Keggin-type Polyoxometalates and Pyrazine-2,3-dicarboxylate

Five rare-earth–transition-metal (RE–TM) heterometal organic–inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2⋅n H2O (n≈4; RE=YIII ( 1 ), DyIII ( 2 ), YbIII ( 3 ), and LuIII ( 4 )) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}⋅n H2O ( 5 ; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1–5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210− subunits linked by H2pzda ligands. Interestingly, 1–4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1–5 represent the first monovacant Keggin-type silicotungstates containing both RE–TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3–5 are attributable to the H2pzda ligands.     

含“CCl_3”或“C≡C”基团的酯类化合物的合成与表征

本文合成了六个含“ＣＣｌ３”或“ＣＣ”基团的酯类化合物（［Ｃｌ３ＣＣ（Ｏ）ＯＣＨ２］２１;ｐ－（Ｃｌ３ＣＣ（Ｏ）Ｏ）２Ｃ６Ｈ４２;（Ｃｌ３ＣＣ（Ｏ）Ｏ）３Ｃ３Ｈ５３;（Ｃｌ３ＣＣ（Ｏ）ＯＣＨ２）４Ｃ４;Ｃｌ３ＣＣ（Ｏ）ＯＣＨ２ＣＣＨ５;Ｃ６Ｈ５Ｃ（Ｏ）ＯＣＨ２ＣＣＨ６）并对其进行了Ｃ／Ｈ分析、ＩＲ、１ＨＮＭＲ等项表征,对化合物５、６进行了质谱分析。     

Photoacoustic spectroscopy study of neodymium complexes with alanine,valine, phenylalanine and tryptophan

Neodymium complexes with amino acids: Nd(Ala)(3)Cl(3).3H(2)O, Nd(Val)(3)Cl(3).3H(2)O, Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O (Ala: L-alanine, Val: L-valine, Phe: L-phenylalanine, Trp: L-tryptophan) are synthesized and their photoacoustic (PA) spectra are reported. The nephelauxetic ratio beta, bonding parameter b(1/2) and Sinha parameter delta are calculated based on their PA spectra. The variation of these parameters and correlation of them with the nature of metal-ligand bonding are discussed. The PA intensity analysis of the f-f transitions of neodymium ion is carried out by calculating the intensity branching vector. The environmental effect on the f-f transitions of neodymium ion is also studied. The branching vectors of the f-f transitions of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O are similar, which indicates the perturbation of the two ligand fields is similar. The branching vectors of energy levels 4G(5/2)+(2)G(7/2) of Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O increase remarkably compared with those of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O. As the degree of covalency increases, the oscillator strength of the hypersensitive transition exhibits a corresponding increase. The relaxation process of Nd(Ala)(3)Cl(3).3H(2)O is established through its PA and electron absorption spectroscopy (EAS). A method used to resolve the PA amplitude spectrum is suggested. With the phase spectrum, PA absorption bands of Nd(Trp)(3)Cl(3).3H(2)O are resolved well in the region of ligand absorption.