稀土(III)及铜(II)、锌(II)有机磷（膦）酸酯配合物的晶体结构和振动光谱研究

本文包括标题配合物的结构和振动光谱两部分，共涉及了M(DMP)_n {n=2.3, M=2a, Nd, Cu. Zn}, Ln(DPP)_3{2n=2a-2u, Y}和Ln(BBP)_3 {Ln=La-Lu. Y}三类三十四个配合物。在结构方面，首次测定了Zn(DMP)_2和Cu(DMP)_2呈现出链状配位高聚结构，而La(DMP)_3, La(DMP)_3则为平面网状配位高聚结构。在Zn(DMP)_2, La(DMP)_3和Nd(DMP)_3中，配体以对称“O－P���O”桥键与金属原子配位，在相邻金属原子间形成双桥键。在Zn(DMP)_2中，每个Zn原子通过“O－P���O”双桥键与另两个Zn原子连接，Zn原子配位数为4，配位多面体为四面体构型；在La(DMP)_3和Nd(DMP)_3中，每个稀土原子通过“O－P���O”双桥键与另外三个稀土原子相连接，稀土原子的配位数为6，配位多面体LnO_6为八面体构型。在Cu(DMP)_3中， 配体以对称和非对称“O－P���O”桥键两种形式存在，其中非对称配位的配体形成为“Cu-O-P_O-Cu"-Cu，在铜原之间形成了一个单氧桥键。每个Cu原子通过双“O－P���O”桥键以及双单氧原子桥键与另外三个Cu原子相连接，Cu原子配位数为5，配位多面体为四角锥构型。在振动光谱方面，得到了上述配合物较为完整的光谱数据，并对主要光谱带进行了归属，如V_(M-O), V_(PO_2), V_(P-O(c)),VC-O, VP-C及σ_PO_2等。在稀土配合物中，稀土配位键的伸缩振动V_(vn-o)位于250cm~(-1)附近。V_(Cu)和V_(Zn-o)，在Cu(DMP)_2和Zn(DMP)_2中，分别为(412cm~(-1), 370cm~(-1))和(393cm~(-1), 386cm~(-1))。V_(as)PO_2和V_sPO_2，在配合物振动光谱中，分别在1130－1249cm~(-1)区和1084－1156cm~(-1)区。在稀土配合物中，VL_(n-o), V_(as)PO_2频率值，随镧系收缩逐渐递增。在Cu(DMP)_2红外谱中，非对称配体和对称配体的V_(as)PO_2和V_sPO_2, 分别为(1249cm~(-1)，1156cm~(-1))及(1177cm~(-1)，1090cm~(-1))，其劈裂值△V(V_(as)PO_2-V_sPO_2)为93cm~(-1)和87cm~(-1)。通过对配合物的常温和低温红外光谱的比较，确认了La(DMP)3和Nd(DMP)_3的176cm~(-1)、Ln(DPP)_3和Ln(BBP)_3的150cm~(-1)附近吸收为晶格振动。Ln(DPP)_3、Ln(BBP_3)的光谱性质与Ln(DMP)_3相似，我们认为它们之间具有相同的骨架结构－平面网状配位高聚结构。

铜（III）及相关化合物的合成和性质的研究，稀土复合氟化物电性、氧敏和氢敏性质

本论文包括两部分内容。第一部分为“Cu(III)及相关化合物的合成和性质的研究”；第二部分为“稀土复合氟化物的电性、氧敏和氢敏性质”。第一部分的主要内容有：1.制备了Na_4H[Cu(H_2TeO_6)_2]·17H_2O和Na_4K[Cu(HIO_6)_2]·12H_2O的Cu(III)单晶配合物。2.在比较相应的Cu(II)化合物的条件下，详细地研究了这二个Cu(III)配合物的电子光谱和Cu2p���电子能谱，由于价态升高，场强参数增大，Cu(III)化合物的d-d跃迁相对于Cu(II)化合物d-d跃迁，发生“蓝移”。3.成功地实现了用O_3和电化学方法对强碱溶液中Cu(II)配合物的氧化，获得了二个新的Cu(III)固态配合物Ba_4K[Cu(H_2TeO_6)_2] (OH)_4·6H_2O和Ba_3K[Cu(HIO_6)_2] (KOH)_(0.5)(OH)_2·8H_2O利用化学分析、磁学性质、电子光谱和Cu2p XPS，对这二个化合物进行了表征。4.对BaCuO_(2.5)的合成、电学性质、磁学性质、Cu(III) ESR和Cu2p XPS进行了研究。5.以Na_4K[Cu(HIO_6)_2]·12H_2O和BaCuO_(2.5)为参照物，用电子光谱和Cu2p XPS，确认了YBa_2Cu_3O_(7-5)中的高价态的铜。6.考察了以Cu（III）化合物作为Cu部分原料所合成的YBCO系超导材料的电学性质。第二部分的主要内容有：1.测试了元件“BiF_3(Bi)/Ce_(0.95)Ca_(0.05)F_(2.95)/Pt”的氧敏、氢敏等性能。从室温到130 ℃，元件的氧敏机理为“双电子反应”，电动势（EMF）与氧分压遵循Nernst关系式。室温时，元件对空气中100Pa或1000Pa氢气的响应时间仅为15秒或短于5秒；氢分压在16Pa～1000Pa范围内，EMF与氢分压的对数呈线性关系，斜率为-116mV/decade, 敏感机理表现为“混合电极电势”。元件具有良好的氢敏性能，并有一定的选择性。2.合成并测试了La_(1-x)Pb_xF_(3-x)(X = 0.00 ～ 0.15)的电导率，La_(0.95)Pb_(0.05)F_(2.95)的电导率最高，比LaF_3高约一个数量级。以La_(0.95)Pb_(0.05)F_(2.95)为固体电解质材料，Pd或Pt为敏感电极，BiF_3(Bi)或PbF_2(Pb)为参比电极，制成了四个元件。其中，“BiF_3(Bi)/La_(0.95)Pb_(0.05)F_(2.95)/Pt”具有最好的氧敏、氢敏性能。从室温到150 ℃，元件的EMF与1gPo_2附合Nernst关系式。150 ℃时，元件对氧气的响应时间仅为80秒。室温下，元件对空气中100Pa或1000Pa氢气的响应时间仅为75秒或15秒，元件的电动势EMF与氢分压的关系可表示为“E=E_o-96lgP_(H2)(mV)”。元件对CO有较差的敏感性能，而对空气中甲烷、乙烷或乙炔（≤1000Pa）不具敏感性能。3.合成并测试了Ln_(1-x)Pb_xF_(3-x)(Ln=Ce、Pr、Nd和Gd、Dy、Ho、Yb)的电性。前四个系列为离子导体材料，后三个系列可能为P���半导体。随着Ln原子序数增大，LnF_3导电性能变差；La~(3+)、Ce~(3+)、Pr~(3+)、Nd~(3+)与Pb~(2+)离子半径差异较小，LnF_3和PbF_2可以形成固溶体；而Gd~(3+)、Dy~(3+)、Ho~(3+)、Yb~(3+)与Pb~(2+)离子半径差异较大，LnF_3和PbF_2难以形成固溶体。

Guest inducing p-sulfonatocalix[4] arene into three-dimensional capsule architecture and a mixed A-B double layer framework

The reactions of sodium p-sulfonatocalix[4]arene (Na5L) and terbium/europium(III) chloride in the presence of pyrazine-N,N'-dioxide (PNNO) in aqueous solutions gave the crystalline complexes 1 and 2. Both structures contain molecular capsules of p-sulfonatocalix[4] arene with PNNO as guest molecules in the cavity of the calix[4]arenes. The molecular capsules are connected through sodium and terbium (or europium) centers forming a three-dimensional framework.

Synthesis, structural characterization, and ethylene polymerization behavior of the vanadium(III) complexes bearing salicylaldiminato ligands

Vanadium(III) complexes bearing salicylaldiminato ligands (2a-k) [RN=CH(Ar0)]VCl2(THF)2 (Ar C61714, R = Ph, 2a; p-CF3Ph, 2b; p-CH3Ph, 2c; 2,6-Me2Ph, 2d; 2,6-iPr2Ph, 2e; cyclohexyl, 2f; Ar = C6H3tBu(2), R = Ph, 2g; 2,6-iPr2Ph, 2h; Ar = C6H2tBU2(2,4), R = Ph, 2i; 2,6-iPr2Ph, 2j; Ar = C6H2Br2, R = Ph, 2k) were prepared from VC13(THF)3 by treating with 1.0 equiv of (RN=CH)ArOH in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA).

Injection, Transport, Absorption and Phosphorescence Properties of a Series of Blue-Emitting Ir(III) Emitters in OLEDs: a DFT and Time-Dependent DFT Study

Quantum-chemistry methods were explored to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of blue-emitting Ir(III) complexes {[(F-2-ppy)(2)Ir(pta -X/pyN4)], where F-2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = phenyl(1); p-tolyl (2); 2,6-difluororophenyl (3); -CF3 (4), and pyN4 = pyridine-1,2,4-tetrazolate (5)}, which are used as emitters in organic light-emitting diodes (OLEDs). The mobility of hole and electron were studied computationally based on the Marcus theory. Calculations of Ionization potentials (IPs) and electron affinities (EAs) were used to evaluate the injection abilities of holes and electrons into these complexes.

A {Co-32} Nanosphere Supported by p-tert-Butylthiacalix[4]arene

Calixarene-capped Co-32 clusters are constructed by a sodalite Co-24(II) cage and an encapsulated Co-8(III) cube. The spherical units are arranged into three isomeric structures, two of which are stacked by the bcc lattices and the third of which is assembled by the cubic closest packing of the spherical units.

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

Novel vanadium(III) complexes with bidentate N,N-chelating iminopyrrolide ligands: synthesis, characterization and catalytic behaviour of ethylene polymerization and copolymerization with 10-undecen-1-ol

A series of novel vanadium(III) complexes bearing iminopyrrolide chelating ligands [2-(RN=CH)C4H3N]V(THF)(2)Cl-2 (2a: R = cyclohexyl; 2b: R = Ph; 2c: R = 2,6-iPr(2)C(6)H(3); 2d: R = p-CF3C6H4; 2e: R = C6F5) have been synthesized and characterized. Single-crystal X-ray diffraction revealed that complexes 2a, 2c and 2e adopt an octahedral geometry around the vanadium center. In the presence of Et2AlCl as a co-catalyst, these complexes displayed high catalytic activities up to 48.6 kg PE mmol(V)(-1) h(-1) bar(-1) for ethylene polymerization, and produced high molecular weight polymers. 2a-e/Et2AlCl catalytic systems were tolerant to elevated temperature (70 degrees C) and yielded unimodal polyethylenes, indicating the single site behaviour of these catalysts. By pre-treating with equimolar amounts of alkylaluminums, functional alpha-olefin 10-undecen-1-ol can be efficiently incorporated into polyethylene chains. 10-Undecen-1-ol incorporation can easily reach 15.8 mol% under the mild conditions.

Four New Lanthanide-Nitronyl Nitroxide (Ln(III)=Pr-III, Sm-III, Eu-III, Tm-III) Complexes and a Tb-III Complex Exhibiting Single-Molecule Magnet Behavior

Five new complexes based on rare-earth-radical [Ln(hfac)(3)(NIT-5-Br-3py)](2) (Ln=Pr (1), Sm (2), Eu (3), Tb (4), Tm (5); hfac = hexafluoroacetylacetonate; NIT-5-Br-3py = 2-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)-5-bromo-3-pyridine) have been synthesized and characterized by X-ray crystal diffraction. The single-crystal structures show that these complexes have similar structures, in which a NIT-5-Br-3py molecule acts as a bridging ligand linking two Ln(III) ions through the oxygen atom of the N-O group and nitrogen atom from the pyridine ring to form a four-spin system. Both static and dynamic magnetic properties were measured for complex 4, which exhibits single-molecule magnetism behavior.

Two-Step Spin-Transition Iron(III) Compound with a Wide [High Spin-Low Spin] Plateau

A new iron(III) coordination compound exhibiting a two-step spin-transition behavior with a remarkably wide [HS-LS] plateau of about 45 K has been synthesized from a hydrazino Schiff-base ligand with an N,N,O donor set, namely 2-methoxy-6-(pyridine-2-ylhydrazonomethyl) phenol (Hmph). The single-crystal X-ray structure of the coordination compound {[Fe(mph)(2)](ClO4)(MeOH)(0.5)(H2O)(0.5)}(2) (1) determined at 150 K reveals the presence of two slightly different iron(III) centers in pseudo-octahedral environments generated by two deprotonated tridentate mph ligands. The presence of hydrogen bonding interactions, instigated by the well-designed ligand, may justify the occurrence of the abrupt transitions. 1 has been characterized by temperature-dependent magnetic susceptibility measurements, EPR spectroscopy, differential scanning calorimetry, and Fe-51 Mossbauer spectroscopy, which all confirm the occurrence of a two-step transition. In addition, the iron(III) species in the high-spin state has been trapped and characterized by rapid cooling EPR studies.

Separation of scandium(III) from lanthanides(III) with room temperature ionic liquid based extraction containing Cyanex 925

The separation of Sc(III) from Y(III), La(III) and Yb(III) in [C(8)mim][PF6] containing Cyanex 925 has been investigated, and is reported in this paper. A cation exchange mechanism of Sc(III) in [C(8)mim][PF6] and Cyanex 925 is proposed by study of the influence of anionic and cationic species on the extraction. The coefficient of the equilibrium equation of Sc(III) was confirmed by slope analysis of log D-Sc vs log [Cyanex 925], and the loading capacity also confirmed the stoichiometry of Cyanex 925 to Sc(III) was close to 3:1. Infrared data for Cyanex 925 saturated with Sc(III) in [C(8)mim][PF6] indicated strong interaction between P=O of Cyanex 925 and Sc(III). In addition, the relationship between log D-Sc and temperature showed that temperature had little influence on the extraction process, and the resulting thermodynamic parameters indicated that an exothermic process was involved.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.

Properties of complex of Tb(III) and poly(N-isopropylacrylamide)-g-poly(N-isopropylacrylamide-co-styrene) core-shell nanoparticles

We successfully prepared a new kind of thermoresponsive and fluorescent complex of Tb(III) and PNIPAM-g-P(NIPAM-co-St) (PNNS) core-shell nanoparticle. It was found that Tb(III) mainly bonded to 0 of the carbonyl groups of PNNS, forming the novel (PNIPAM-g-P(NIPAM-co-St))-Tb(III) (PNNS-Tb(III)) complex. The maximum emission intensity of the complex at 545 nm is enhanced about 223 times comparing to that of the pure Tb(III). The intramolecular energy transfer efficiency from PNNS to Tb(III) reaches 50%. When the weight ratio of Tb(III) and the PNNS-Tb(III) complex is 1.2 wt.%, the enhancement of the emission fluorescence intensity at 545 nm is highest.

Surface renewable graphite organosilicate composite electrode containing indium(III) hexacyanoferrate(II/III)

Indium(III) hexacyanoferrate(II/III) (InHCF) supported on graphite powder was prepared using the in situ chemical deposition procedure and subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive graphite organosilicate composite. The composite was used as the electrode material to fabricate a three-dimensional InHCF-modified electrode. InHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The chemically modified electrode can electrocatalyze the oxidation of thiosulfate, and exhibits a good repeatability of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.

Synthesis and crystal structure of a polymeric erbium(III)-sodium(I) coordination complex of picolinic acid N-oxide

A new Er(III)-Na(I) coordination polymer of stoichiometry [NaEr2L5(H2O)(6)(NO3)](NO3). 3.5H(2)O (HL = picolinic acid N-oxide) has been synthesized and characterized by single-crystal X-ray analysis. Crystals are triclinic, P (1) over bar with a = 9.823(2), b = 12.453(2), c = 20.643(4) Angstrom; alpha = 98.49(3), beta = 101.40(3), gamma = 108.69(3)degrees; V = 2284(1) Angstrom(3); Z = 2. Of the two independent eight-coordinate erbium(III) ions in this complex, one is surrounded by four bidentate chelating L ligands, and the other by one bidentate chelating L ligand, four aqua ligands and two anti-carboxylate oxygen atoms from two neighboring [ErL4] units. The sodium(I) ion is in a distorted octahedral environment, being coordinated by a unidentate nitrate anion, three aqua ligands and two anti-carboxylate oxygen atoms from two adjacent [ErL4] units. The complex is built from zigzag chains of syn-anti carboxylate-bridged erbium(III) moieties directed in the a direction, which are cross-linked pairwise by aqua-bridged dimeric sodium(I) units. The resulting composite polymeric chains are further connected by hydrogen bonds to form a three-dimensional network.