Al柱层状钛铌酸盐的制备

本文采用分步交换法,首次将[Al~1~3O~4(OH)~2~4(H~2O)~1~2]^7^+Keggin离子交换进入到层状金属钛铌酸盐(KTiNbO~5)的层间.通过焙烧,制备了以Al~2O~3 为柱的层状金属化合物.该化合物具有较高的热稳定性(>500℃)和比较大的层间距(d=1.34nm,500℃)     

氧化铝柱层状铌酸盐的制备

本文以HNb~3O~8为例, 进一步探讨了用分步交换法来制备氧化铝柱层状金属氧化物的可行性。首次成功地将[Al~13O~4(OH)~24(H~2O)~12]^7+Keggin离子交换进入到层状金属铌酸(HNb~3O~8)的层间。通过焙烧, 制备了首例以氧化铝为柱的层状金属铌酸盐。该化合物具有很高的热稳定性(>700℃)和比较大的层间距(d=1.18nm,700℃), 讨论了不同层板性质对产物结构和性能的影响。     

trans-[(en)~2(NO~2)Co(O~2CC~5H~5N)]^2^+/Fe(Ⅱ)间电子转移反应动力学及机理研究

合成了新型Co(Ⅲ)配合物trans-[(en)~2(NO~2)Co(O~2CC~5H~5N)](ClO~4)~2, 并通过紫外可见光谱、红外光谱、元素分析和X射线单晶衍射分析进行了表征。同时分别以[Fe(CN)~6]^4^-和[Fe(CN)~5(H~2O)]^3^-作为还原剂, 考察了该配合物被还原的反应动力学行为。结果表明两反应体系分别按外配位界机理和内配位界机理进行电子传递。在25℃, Ⅰ=0.5mol·L^-^1,trans-[(en)~2(NO~2)Co(O~2CC~5H~5N)]^2^+/[Fe(CN)~6]^4^-反应体系的前驱配合物离子对形成常数Q~i~p=29mol^-^1·L, 电子转移速率常数k~e~t=2.4×10^-^4s^-^1,电子转移过程的活化焓△H^≠~e~t和活化熵△S^≠~e~t分别为1.2×10^2kJ·mol^-^1和5.0×10^2J·mol^-^1·K^-^1。在40℃, pH=8.0, Ⅰ=0.1mol·L^-^1,trans-[(en)~2(NO~2)Co(O~2CC~5H~4N)]^2^+/[Fe(CN)~5(H~2O)]^3^-反应体系前驱双核配合物分子内电子转移速率常数为7.0×10^-^5s^-^1。最后讨论了分子轨道对称性, 两金属中心氧化还原电势差等因素对电子转移速率的影响。     

三硫氰酸根三乙二胺合镉(II)钾(I)的晶体结构

含钾和二价金属离子的双金属硫氰酸根配合物的晶体结构研究已有一些报道。在K~2Pb(SCN)~4^[^1^]和K~2Cd(SCN)~4.2H~2O^[^2^]这两个化合物中,晶体结构都是由K^+和M(SCN)~4^2-组成。本文报道了Cd(en)~3K(NCS)~3的晶体结构,其基本构型与上述两个化合物有显著的不同(en为乙二胺)。     

钌铁双核配合物的合成及猝灭[Ru(bpy)~3]^2^+发光过程研究

合成了含二氮芴和联吡啶等配体的一系列新型钌铁双核配合物:[(C~1~0H~6N~2)C=N-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,[(C~1~0H~6N~2)C=N--C~6H~4-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,[(C~1~0H~6N~2)C=N-C~6H~4-C~6H~4-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,并对其进行了光谱表征,通过对该类配合物的循环伏安和发光光谱研究,讨论其激发态的氧化还原性和对[Ru(bpy)~3]^2^+发光过程的猝灭作用.研究表明猝灭过程为扩散控制的双分子交换能量传递     

MAP-H~2O~2-HPR伏安酶联免疫分析新体系和光谱及电化学研究

提出了间氨基酸(MAP)-H~2O~2-辣根过氧化物酶(HRP)伏安酶联免疫分析新体系.本方法以线性扫描二阶导数伏安法检测HRP催化H~2O~2氧化MAP的产物,用于游离HRP和各种HRP标记物的测定,灵敏度均高于经典的ELISA显色光度法.测定游离HRP的线性范围为1.0x10^-^8-1.0x10-6/L,检测限达3.8x10^-^9g/L.制备出了HRP催化H~2O~2氧化MAP的产物纯品并应用电化学分析,高效液相色谱,元素分析,紫外-可见光谱,红外光谱,^1H核磁共振谱,^1^3C核磁共振谱及质谱等技术对体系酶促反应进行了深入的研究.在选择的酶促反应条件下,生成的产物为2-氨基-5-[(3-差苯基)]-2,5-环己烯基-1,4-二酮.提出了酶催化反应机理及其产物的电极还原过程。     

MAP-H~2O~2-HPR伏安酶联免疫分析新体系和光谱及电化学研究

提出了间氨基酸(MAP)-H~2O~2-辣根过氧化物酶(HRP)伏安酶联免疫分析新体系.本方法以线性扫描二阶导数伏安法检测HRP催化H~2O~2氧化MAP的产物,用于游离HRP和各种HRP标记物的测定,灵敏度均高于经典的ELISA显色光度法.测定游离HRP的线性范围为1.0x10^-^8-1.0x10-6/L,检测限达3.8x10^-^9g/L.制备出了HRP催化H~2O~2氧化MAP的产物纯品并应用电化学分析,高效液相色谱,元素分析,紫外-可见光谱,红外光谱,^1H核磁共振谱,^1^3C核磁共振谱及质谱等技术对体系酶促反应进行了深入的研究.在选择的酶促反应条件下,生成的产物为2-氨基-5-[(3-差苯基)]-2,5-环己烯基-1,4-二酮.提出了酶催化反应机理及其产物的电极还原过程。     

五,六硝酸根合稀土(Ⅲ)酸4-[2-(3-硝基-4-甲氧基苯基)乙烯基]-1-甲基吡啶配合物的合成及性质

合成了通式为(C~1~5H~1~5N~2O~3)~xRE(NO~3)~y(当RE=La～Gd时,x=3,y=6,RE=Tb～Lu,Y时,x=2,y=5)的一个系列十五种五,六硝酸根合稀土(Ⅲ)酸4-[2-(3- 硝基-4-甲氧基苯基)乙烯基]-1-甲基吡啶配合物.通过元素分析, 紫外光谱, 红外光谱,^1H核磁共振谱,热重-差热分析,摩尔电导和X 射线粉末衍射分析等对各配合物的结构和性质进行了表征,并对影响其组成变化的因素作了初步探讨     

一个新的超大铈锑钨酸盐阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4

合成了一超大铈锑钨酸盐[Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O,用X射线单晶衍射法及元素分析确定了其结构。其晶胞参数为：a=1.8908(6)nm,b=2.0032(14)nm,c=2.8653(12)nm,α=86.95(6)°,β=75.68(3)°,γ=67.52(5)°,V=9.706(9)nm^3,空间群P1。在杂多阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4中,四个β-B-(SbW~9O~3~3)^9^-是通过一个大的中心集团[Ce~3Sb~4W~2O~8(H~2O)~1~0]^1^7^+连接起来的,中心集团中含有两个桥连{WO~2(H~2O)}基,三个Ce(Ⅲ)离子和一个{Sb~4O~4}基团。三个Ce(Ⅲ)离子的配位数均为9,Ce(1)和Ce(3)的配位环境相同,但不同于Ce(2)的配位环境,四个{SbW~9O~3~3}中的三个参与了向Ce(Ⅲ)的配位。两个{SbW~9O~3~3}中的四个氧,三个水分子中的三个氧,{Sb~4O~4}中的一个氧及一个桥连{WO~2(H~2O)}中的一个氧向Ce(1)[或Ce(3)]配位;两个{SbW~9O~3~3}中的四个氧,两个水分子中的两个氧,{Sb~4O~4}中的一个氧及两个桥连{WO~2(H~2O)}中的两个氧向Ce(2)配位。在{Sb~4O~4}中,四个Sb原子的中心构成了一四面体。该离子属C~s点群,Sb(5),Sb(8)和Ce(2)所在的平面是其对称面。     

新型二维草酸根桥联配合物 {[Cu(en)~2]~4[KFe(C~2O~4)~3]~4}~n的合成、结构 和磁性

合成了一个新型草酸根桥联的二维配合物{[Cu(en)~2]~4[KFe(C~2O~4)~3]~4}~n,并进行了晶体结构测试和磁性研究。晶体结构分析显示:K^+离子为罕见的八配位环境,2个C~2O~4^2^-和2个或1个K^+离子长程桥联2个Fe^Ⅲ离子,形成一个二维网状的[KFe(C~2O~4)~3]~n^2^n^-骨架,[Cu(en)~2]^2^+单元通过(en)N-H...O(C~2O~4)氢键与[KFe(C~2O~4)~3]~n^2^n^-骨架连接。变温磁化率测量表明:Fe^Ⅲ与Fe^Ⅲ间存在着弱的磁相互作用,J=-0.17cm^-^1。     

有机-无机复合杂多化合物的合成、结构及表征

利用常规水溶液法制备了三种基于饱和Keggin结构阴离子的有机-无机复合杂多化合物[Pr(pydc)(H2O)6]2H[PMo12O40]·4H2O(1)、[Nd(pydc)(H2O)6]2H[PMo12O40]·4H2O(2)和[Tb(pydc)(H2O)6]2H[PMo12O40]·4H2O(3)(pydc=2,6...     

Effect of counteranion X on the spin crossover properties of a family of diiron(II) triazole complexes [Fe(II)2(PMAT)2](X)4

Seven diiron(II) complexes, [Fe(II)(2)(PMAT)(2)](X)(4), varying only in the anion X, have been prepared, where PMAT is 4-amino-3,5-bis{[(2-pyridylmethyl)-amino]methyl}-4H-1,2,4-triazole and X = BF(4)(-) (1), Cl(-) (2), PF(6)(-) (3), SbF(6)(-) (4), CF(3)SO(3)(-) (5), B(PhF)(4)(-) (6), and C(16)H(33)SO(3)(-) (7). Most were isolated as solvates, and the microcrystalline ([3], [4]·2H(2)O, [5]·H(2)O, and [6]·?MeCN) or powder ([2]·4H(2)O, and [7]·2H(2)O) samples obtained were studied by variable-temperature magnetic susceptibility and Mo?ssbauer methods. A structure determination on a crystal of [2]·2MeOH·H(2)O, revealed it to be a [LS-HS] mixed low spin (LS)-high spin (HS) state dinuclear complex at 90 K, but fully high spin, [HS-HS], at 293 K. In contrast, structures of both [5]·?IPA·H(2)O and [7]·1.6MeOH·0.4H(2)O showed them to be [HS-HS] at 90 K, whereas magnetic and M?ssbauer studies on [5]·H(2)O and [7]·2H(2)O revealed a different spin state, [LS-HS], at 90 K, presumably because of the difference in solvation. None of these complexes undergo thermal spin crossover (SCO) to the fully LS form, [LS-LS]. The PF(6)(-) and SbF(6)(-) complexes, 3 and [4]·2H(2)O, appear to be a mixture of [HS-LS] and [HS-HS] at low temperature, and undergo gradual SCO to [HS-HS] on warming. The CF(3)SO(3)(-) complex [5]·H(2)O undergoes gradual, partial SCO from [HS-LS] to a mixture of [HS-LS] and [HS-HS] at T(1/2) ≈ 180 K. The B(PhF)(4)(-) and C(16)H(33)SO(3)(-) complexes, [6]·(1)/(2)MeCN and [7]·2H(2)O, are approximately [LS-HS] at all temperatures, with an onset of gradual SCO with T(1/2) > 300 K.     

Synthesis and structure of asymmetric zirconium-substituted silicotungstates, [Zr6O2(OH)4(H2O)3(beta-SiW10O37)3]14- and [Zr4O2(OH)2(H2O)4(beta-SiW10O37)2]10-

The reaction of ZrCl4 with [gamma-SiW10O36]8- in a potassium acetate buffer results in two different products depending on the reactant ratios. The trimeric species [Zr6O2(OH)4(H2O)3(beta-SiW10O37)3]14- (1) consists of three beta23-SiW10O37 units linked by an unprecedented Zr6O2(OH)4(H2O)3 cluster with C1 point group symmetry. The dimeric species [Zr4O2(OH)2(H2O)4(beta-SiW10O37)2]10- (2) consists of beta22- and beta12-SiW10O37 units sandwiching a Zr4O2(OH)2(H2O)4 cluster, which also has C1 symmetry. Polyanion 1 contains more zirconium centers than any other polyoxometalate known to date.     

一个新的铈砷钨酸盐大阴离子[As4W40O140Ce(H2O)5]^25-

合成了一新的铈砷钨酸盐[As4W40C140Ce(H2O)5]Na25·63H2O,用X射线单晶衍射法及元素分析确定了其结构。其晶胞参数为：a=3.1252(8)nm,b=2.2656(6)nm,c=1.3973(9)nm,α=β=γ90°,V=9.893(7)nm^3,空间群P21/m21/m2/n。在聚阴离子[As4W40O140Ce(H2O)5]^25-中,四个桥连WO6八面体通过相互共享两个顺式氧串联四个B-α-(AsW9O33)^9-形成环配体(As4W40O140)^28-的基本框架,四个B-α-(AsW9O33)^9-并不处在一个平面上,而是上下交错分布的。中心离子Ce(Ⅲ)未完全填充在(As4W40O140)^28-中具有八齿配位能力的S1洞穴中,而是四个桥连的WO6八面体各提供一个端基氧向Ce(Ⅲ)配位,另有五个水分子向Ce(Ⅲ)配位,Ce(Ⅲ)离子的配位数为9,该离具有C2v对称性。     

Copper-linked hexaniobate lindqvist clusters-variations on a theme

Four new one-dimensional materials and one dimer complex based on the linkage of [Nb6O19] clusters and [CuLx] (L=ethylenediamine (en), NH3, H2O) assemble under ambient conditions. These phases include the following: Rb4[Cu(en)2(H2O)2]3[(Nb6O19H2)2Cu(en)2].24H2O (1), space group P; [Cu(en)2(H2O)2]2[(Nb6O19H2)Cu(en)2].14H2O (2), space group P; Rb2[Cu(NH3)2(H2O)4][Cu(NH3)4(H2O)2]2{[Nb6O19][Cu(NH3)]2}(2).6H2O (3), space group P; {[Nb6O19][Cu(NH3)2(H2O)]2[Cu(H2O)4]2}.3H2O (4), space group P2/n; and {[Nb6O19][Cu(NH3)2(H2O)]2[Cu(H2O)4]2} (5), space group C2/m. All structures have been solved by single-crystal methods, and compounds 1-5 were characterized by thermogravimetric analysis, Fourier transform IR, chemical analysis, and magnetic measurements. It has been demonstrated that the conformation, charge, and geometry of the [Nb6O19]-[CuLx] chains can be modulated by varying the type and amount of the [CuLx]2+ species. The charge balance is provided by mixed Rb+/[CuLx]2+ or [CuLx]2+ cations only for structures 1-3, whereas 4 and 5 are neutral chains with no counterions. There are weak antiferromagnetic Cu2+-Cu2+ interactions in all phases. Compounds 2-5 represent the first examples in which the [Nb6O19] Lindqvist ion forms extended solids rather than dimers or decorated monomers when reacted with transition-metal, cationic complexes.     

由Keggin型簇和过渡金属配合物构筑的杂多钨酸盐锯齿链的合成和结构

采用水热法合成了一维锯齿链状的有机-无机杂化杂多钨酸盐[Cu（en）2（H2O）]{[Cu（en）2（H2O）][Cu（en）2]（α-SiW12O40）}（OH）2·H2O（记作1;en=1,2-乙二胺）;利用元素分析、红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1属于三斜晶系,P-1空间群;其晶格参数为：a=1.297 6（6）nm,b=1.473 5（7）nm,c=1.909 9（9）nm,α=86.736（8）°,β=88.833（8）°,γ=74.840（8）°,V=3.519（3）nm3,Z=2.就分子结构而言,化合物1由一个常见的Keggin型多阴离子[α-SiW12O40]4-、两个不同的铜配位阳离子[Cu（en）2（H2O）]2＋和[Cu（en）2]2＋、一个游离的铜配位阳离子[Cu（en）2（H2O）]2＋、两个氢氧根离子和一个结晶水组成;相邻的[α-SiW12O40]4-多阴离子通过两个配位阳离子[Cu（en）2）]2＋相连,形成一维锯齿链状结构.     

Si取代Keggin型多酸催化光解水产氢机理

本文采用DFT和TD-DFT方法研究了Keggin型多酸[SiW12O40]4-光催化劈裂水产氢气机理。计算结果显示反应主要包括四个步骤：(i) 光激发,(ii) 电荷转移和生成单电子还原(OER)中间体,(iii) 生成双电子还原(TER)中间体,(iv)氢气从多酸表面解离和催化剂重生。当第一个电子从甲醇转移到多酸后,后续反应存在均为热力学上有利的放热途径,并推动第二个电子从甲醇自由基,H[SiW12O40]4-或[SiW12O40]5-转移到OER中间体H[SiW12O40]4-或[SiW12O40]5-生成TER中间体[SiW12O40]6-,H[SiW12O40]5-或H2[SiW12O40]4-,并伴随着H2产生。耦合的电子和质子转移路径在能量上最有利。甲醇和水分子的参与有利于H2产生。多酸在整个催化循环中,扮演了光敏剂、催化剂、电子的受体和给体。     

Formation of p-phenylenediamine-crown ether-[PMo12O40]4- salts

Electron transfer from the electron donor of p-phenylenediamine (PPD) to the electron acceptor of (H+)3[PMo12O40]3- forms a one-electron-reduced Keggin cluster of [PMo12O40]4-, bearing a S = 1/2 spin, while proton transfer from the proton donor of (H+)3[PMo12O40]3- to the proton acceptor of PPD yielded mono- and diprotonated cations of 4-aminoanilinium (HPPD+) and p-phenylenediammonium (H2PPD2+). By introduction of crown ether receptors during the crystallization process, supramolecular cations of (HPPD+)(crown ethers) and/or (H2PPD2+)(crown ethers) were successfully introduced into three new alpha-[PMo12O40]4- salts of (H2PPD2+)2([12]crown-4)4[PMo12O40]4- (1), (HPPD+)4([15]crown-5)4[PMo12O40]4- (2), and (HPPD+)2(H2PPD2+)([18]crown-6)4[PMo12O40]4- (3) as the countercation. The protonated states of PPD and molecular-assembly structures of the supramolecular cations depended on the size of the crown ethers. In salt 3, a novel mixed-protonated state of HPPD+ and H2PPD2+ was confirmed to be complexed in the cation structure. According to the changes in the cation structures, the anion arrangements were modulated from those of the two-dimensional layer for salt 1 to the isolated cluster for salts 2 and 3. The temperature-dependent magnetic susceptibilities of salts 1-3 were consistent with the isolated spin arrangements of [PMo12O40]4-. The electronic spectra of salts 1-3 indicated the intervalence optical transition from pentavalent Mo(V) to hexavalent Mo(VI) ions within the [PMo12O40]4- cluster. Temperature-dependent electron spin resonance spectra of salt 2 revealed the delocalization-localization transition of the S = 1/2 spin at 60 K. The spin on the [PMo12O40]4- cluster was localized on a specific Mo(V) site below 60 K, which was thermally activated with an activation energy of 0.015 eV.     

Room-temperature phosphorescence and energy transfer in luminescent multinuclear platinum(II) complexes of branched alkynyls

A series of luminescent branched platinum(II) alkynyl complexes, [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]C-C6H4C[triple bond]C}3C6H3] (R=C6H5, C6H4OMe, C6H4Me, C6H4CF3, C5H4N, C6H4SAc, 1-napthyl (Np), 1-pyrenyl (Pyr), 1-anthryl-8-ethynyl (HC[triple bond]CAn)), [1,3-{PyrC[triple chemical bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3], and [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-(HC[triple bond]C)C6H3], was successfully synthesized by using the precursors [1,3,5-{Cl(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] or [1,3-{Cl(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3]. The X-ray crystal structures of [1,3,5-{MeOC6H4C[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] and [1,8-{Cl(PEt3)2PtC[triple bond]C}2An] have been determined. These complexes were found to show long-lived emission in both solution and solid-state phases at room temperature. The emission origin of the branched complexes [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] with R=C6H5, C6H4OMe, C6H4Me, C6H4CF3, C5H4N, and C6H4SAc was tentatively assigned to be derived from triplet states of predominantly intraligand (IL) character with some mixing of metal-to-ligand charge-transfer (MLCT) (dpi(Pt)-->pi*(C[triple bond]CR)) character, while the emission origin of the branched complexes with polyaromatic alkynyl ligands, [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] with R=Np, Pyr, or HC[triple bond]CAn, [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3], [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-(HC[triple bond]C)C6H3], and [1,8-{Cl(PEt3)2PtC[triple bond]C}2An], was tentatively assigned to be derived from the predominantly 3IL states of the respective polyaromatic alkynyl ligands, mixed with some 3MLCT (d(pi)(Pt)-->pi*(C[triple bond]CR)) character. By incorporating different alkynyl ligands into the periphery of these branched complexes, one could readily tune the nature of the lowest energy emissive state and the direction of the excitation energy transfer.     

Novel large heteropolymetalate complexes formed from Ni(II) and cryptate [As_4W_(40)O_(140)]~(28-)——Synthesis and structure characterization

Heteropolyoxometalates have received much attention due to their fascinating variety of structures and chemical compositions, and potential applications in catalysis, materials science, environmental protection and medicine[1—5]. The synthesis design, structure properties of novel large polyoxometalates and derivatives of known polyoxometalates are interesting and remain a challenge. Several derivatives of big cyclic anion [(B--AsO3W9O30)4(WO2)4]28- 揂s4W40?have been reported[6—8], and th…