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.     

(2-羧基苯氧基)苯-1,2-二羧酸构筑的镧系配合物对苯甲醛和阳离子的荧光传感

采用水热法合成了5个稀土配合物[Sm₂(bdbc)₂(phen)₄](1)和[Ln(bdbc)(phen)(H₂O)][Ln=Eu(2), Gd(3), Tb(4), Dy(5), bdbc=(2-羧基苯氧基)苯-1,2-二羧酸根, phen=1,10-邻菲啰啉]. 配合物1是双核分子, 通过氢键和C—H…π作用进一步构筑成一维超分子结构; 配合物2~5是同构的一维双螺旋结构, 通过氢键和C—H…π作用进一步构筑成三维超分子结构. 配合物1, 2, 4和5呈现了Sm³⁺, Eu³⁺, Tb³⁺和Dy³⁺离子的特征发射, 分别对应于Sm³⁺离子的⁴G_5/2→⁶H_J/2(J=5, 7, 9)、 Eu³⁺离子的⁵D₀→⁷F_J(J=1—4)、 Tb³⁺离子的⁵D₄→⁷F_J(J=6, 5, 4, 3)和Dy³⁺离子的⁴F_5/2→⁶H_J/2(J=15, 13)跃迁. 对配合物4的荧光性质进行了表征, 结果表明, 配合物4可用作荧光探针以检测阳离子和苯甲醛.     

辅助配体调控的荧光Cd-MOFs: 乙酰丙酮的荧光增强和Cr(Ⅵ)的荧光猝灭

将柔性苄氨基三羧酸配体5-(3-羧基-4-甲氧基苄氨基)间苯二甲酸(H₃L)与硝酸镉和不同含氮配体在溶剂热条件下反应, 制得了配合物{[Cd(HL)(bpea)·H₂O]·H₂O·DMF}_n(1)、 {[Cd(HL)(bpp)·H₂O]·2H₂O·DMF}_n(2)和 {[Cd(HL)(dmbpy)]·DMF}_n(3)[bpea=bis(4-pyridyl)ethane; bpp=1,3-bis(4-pyridyl)propane; dmbpy=5,5′-dimethyl-2,2′-bipyridine]. 3个配合物分别表现出有趣的2D→2D穿插结构和一维带状结构. 荧光性质测试结果表明, 所有配合物的荧光均可被Cr₂O₇^2?猝灭, 而在乙酰丙酮的DMF溶液中, 只有配合物1表现出明显的荧光增强. 羧酸配体的柔性、 含氮配体的类型和结构可以调控配合物的结构和荧光性能.     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成、表征以及对H2O2分解的催化活性

合成了通式为K₁₅H₃[Ce(P₂W₁₆VO₆₁)₂]·61H₂O、K₁₅H₄[Ln(P₂W₁₆VO₆₁)₂]·xH₂O(Ln=La³⁺,Pr³⁺,Nd³⁺,Sm³⁺,Eu³⁺,Gd³⁺,Dy³⁺,Yb³⁺)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了研究。该类配合物具有与K₁₆[Ce(P₂W₁₇VO₆₁)₂]·50H₂O类似的结构,对H₂O₂分解有较高的催化活性。     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H₂L)(H₂O)₃]·H₂O·0.5H₄L}_n(1)、{[Co(L)_0.5(4,4'-bpy)]·0.5H₂O}_n(2)和{[Co(L)_0.5(pbmb)(H₂O)]·H₂O}_n(3)(H₄L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6⁴·7·8)(6·7²)的三重穿插网络结构。3是拓扑符号为(4·6²)(4²·6²·8²)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

吡啶二羧酸修饰的稀土嵌入碲钨酸盐的合成及电化学生物识别性质

在乙酸钠水溶液中, 采用微波加热一步自组装策略合成了一系列罕见的2,6-吡啶二羧酸修饰的稀土嵌入Keggin型碲钨酸盐(PTEA)₇H₃K[RE₂(B-α-TeW₉O₃₃)₃W₃O₅(H₂O)₃(HDPA)]·22H₂O[RE=Ce³⁺(1), Pr³⁺(2), Nd³⁺(3), Sm³⁺(4); H₂DPA=2,6-吡啶二羧酸; PTEA=质子化的三乙醇胺]. 化合物1~4的聚阴离子由3个三缺位Keggin型 [B-α-TeW₉O₃₃]^8-构筑块通过1个{RE₂W₃O₅(H₂O)₃(HDPA)}¹³⁺异金属簇连接而成. 该异金属簇中, 2,6-吡啶二羧酸作为四齿配体与2个稀土离子(RE1和RE2)配位形成平面三杂环结构, 且RE1和RE2所在平面与W2, W2A, W16形成的平面互相垂直. 此外, 化合物1可与羧基化多壁碳纳米管(CMWCNT)复合形成1-CMWCNT复合材料. 该复合材料可以作为电极材料构建电化学生物传感器, 用于检测特定的DNA序列.     

基于半刚性乳酸衍生物的单一手性配位聚合物的合成、 结构与性质

在溶剂热反应条件下, 用预先合成的乳酸衍生物(R)-H₂CBA和(S)-H₂CBA分别与含氮辅助配体(E)-1,2-二(4-吡啶基)乙烯(DPEE)和1,4-二(1H-咪唑-1-基)苯(1,4-DIB)组合, 制备出2对不同结构的单一手性配位聚合物[Cd₂((R)-CBA)₂(DPEE)(H₂O)₂]_n(1-D), [Cd₂((S)- CBA)₂(DPEE)(H₂O)₂]_n(1-L), [Cd((R)-CBA)(1,4-DIB)]·H₂O(2-D)和[Cd((S)-CBA)(1,4-DIB)]·H₂O(2-L). 其中1-D和1-L是由梯形Cd-CBA链和DPEE配体连接成的二维框架结构; 而2-D和2-L是三维超分子框架结构, 包含3种不同类型的对映手性螺旋链. 对上述化合物进行了粉末X射线衍射、 热重分析和圆二色谱分析, 并对其荧光性质进行了讨论.     

具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征

在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni₂L₂(bpy)]_n(2)和{[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3)[H₂L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{4²·6⁵·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{4⁸·5⁴·6³}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P\begin{array}{c}\bar{1}\end{array}空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{4⁴·6²}拓扑结构.     

镝(Ⅲ)与酰腙及1,10-菲啰啉多元配合物的晶体结构及荧光性质

在水乙醇混合体系中,首次得到2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄),1,10-菲哕啉(C₁₂H₈N₂,简写作phen)与Dy(NO₃)3·3H₂O的配合物[Dy(C₁₀H₈N₂O₄)(phen)(NO₃)(H₂O)₂]·H₂O.该配合物属单斜晶系,空间群为P2₁/c,晶胞参数a=1.524(3)nm,b=1.1018(19)nm,c=1.468(3)nm,β=92.28(2)°,V=24.63(7)nm³,Z=4,μ=3.100 mm^-1,D_c=1.831g/cm³,F(000)=1340,R=0.0314,wR=0.0660,GOF=O.966.测试结果表明,该单晶结构为镝的9配位配合物,其中一个2-羰基丙酸水杨酰腙分子以羧基氧、酰胺基中的羰基氧和C=N中的氮与Dy³⁺三齿配位,形成两个稳定的共边五元环,一个1,10-菲哕啉分子以二齿方式配位、一个硝酸根和两个水分子也同时参与配位,在空间呈扭曲的单帽四方反棱柱,而在配合物周围还有一个游离的水分子.发光性能测试表明配合物具有很好的荧光性能.     

A unique organic-inorganic hybrid FeⅢ–PrⅢ-included 2-germano-20-tungstate and its electrochemical biosensing properties

An organic-inorganic hybrid Fe^Ⅲ–Pr^Ⅲ-included 2-germano-20-tungstate [Pr（H₂O）₈]₂H₂[Fe₄（H₂O）₄（pca）₄Ge₂W₂₀O₇₂]·34H₂O（Hpca=2-pyridinecarboxylic acid）(1) was hydrothermally prepared. Its polyoxoanion comprises one tetra-Fe^Ⅲ incorporated [Fe₄（H₂O）₄（pca）₄Ge₂W₂₀O₇₂]...     

Studies on Organo-Phosphorus, -Arsenic and -Antimony Polytungstates and Polymolybdates (Ⅶ)——Preparation and Properties of p-Aminophenylarsenic Polymolybdates

In order to investigate the influence of organic groups on the types of organoarsenic polymolybdates, the reations of p-aminophenylarsonic acid with sodium molybdate were tested at pH=3-5. Six salts were prepared and characterized. (1) (CN3H8)4 [(p-NH3C6H4As)2Mo6O25] · H2O, (2) (CN3H6)4 [(p-, NH3C6H4As )2Mo6O25 ] · 6H20, (3) Cs4 [(p-NH3C6H4As)2Mo6O25] · 4H2O, (4) C(CH3)4N]4[(p-NH3C6H4As)2Mo6O25] · 5H2O, (5) [(n-C4H9)4N]3Na[(p-NH3C6H4As)2Mo6O25] · 2H2O, (6) Ba2 NH3C6H4As)2Mo6O25] · 10H2O. The IR, UV spectra, and electrochemical behavior are reported and discussed. They should belong to the same type as that for phenyl derivative or the nitrophenyl derivatives. But the ammo groups can accept protons, so that the anion' s charge decreases. Very similar to the tungsten congener (CN3H6)4[(p-NH3C,H4As)2W6O25] · 4H2O, [(RAs)2Mo6O25]4- type of complexes are formed.     

锌(Ⅱ)配合物的超分子设计及对甲醇蒸气的吸附性能

采用饱和蒸气扩散技术, 将2,4-二羟基苯甲醛缩异烟酰腙(H₂dhbi)配体分别与Zn(ClO₄)₂·6H₂O和Zn(NO₃)₂·6H₂O进行配位作用, 得到2种不同配位模式的金属-有机框架材料[(dhbi)₂Zn₂·8H₂O]_n(1)和{[(dhbi)₂(H₂O)₂Zn₂]·4DMF]}_n(2). 利用X射线单晶衍射、 热分析技术(TG-DTA)和X射线粉末衍射(PXRD)等方法进行了结构表征. 进一步将配位聚合物1和2用于对甲醇分子的吸附性能研究, 结果表明, 化合物1是一种理想的微孔材料, 其对甲醇分子的吸附能力为化合物2的近5倍, 采用PLATON对材料的孔隙体积进行计算得到化合物1和2的孔隙率分别为38.2%和5.5%.     

双(2,4-二甲基戊二烯基)氯化钆的合成及晶体结构

合成双(2,4-二甲基戊二烯基)氯化钆{[2,4-(CH₃)₂C₅H₅]₂GD_cl}₂,并测定了晶体结构.晶体为单斜晶系,P2₁/n空间群.晶胞参数a=0.89141(18)nm,b=1.4486(3)nm,c=1.15925(15)nm,β=92.996(18)°,V=1.4949(4)nm³,Z=3.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

稀土簇基金属有机框架的合成、结构及磁学性质

通过溶剂热法合成出了两种稀土簇基金属有机框架材料:{[Ln_7(OH)_8(HOCH_2COO)_8(H_2O)_3]·Cl_5·3H_2O}_n(Ln=Gd(1),Dy(2))。磁性研究表明,化合物1在低温下具有较大的磁热效应,在3 K、7 T时磁熵变值高达44.4 J/(kg·K),化合物2在不加直流场的情况下具有明显的频率依赖性,表明化合物2具有缓慢弛豫的性质。此外,粉末衍射结果发现,化合物1和2具有非常高的化学稳定性,其可稳定存在于pH值1~14的水溶液及沸水中。结果表明,稀土簇基金属有机框架材料在低温磁制冷方面具有潜在的利用价值。     

Dinuclear molybdenum complexes derived from diphenols: electrochemical interactions and reduced species

The new diphenolato complexes [{Mo(NO){HB(dmpz)₃}Cl}₂Q] where dmpz = 3,5-dimethylpyrazolyl and Q = OC₆H₄(C₆H₄O (n = 1 or 2), OC₆H₄CR=CRC₆H₄O (R = H or Et), and OC₆H₄CH=CHC₆H₄CH=CHC₆H₄O have been prepared and their electrochemical properties (cyclic and differential pulse voltammetry) compared with previously reported analogues where Q = OC₆H₄O, OC₆H₄EC₆H₄O (E = SO₂, CO and S), OC₆H₄ (CO)C₆H₄ C₆H₄(CO)C₆H₄O and 1,5- and 2,7-O₂C₁₀H₆. The electrochemical interaction between the redox centres in the new complexes is very weak, in contrast to that in the 1,4-benzenediolato and naphthalendiolato species. The EPR spectra of the reduced mixed-valence species [{Mo(NO){HB(dmpz)₃}Cl}₂Q]⁻ where Q = 1,3- and 1,4-OC₆H₄O and OC₆H₄SC₆H₄O shows that they are valence-trapped at room temperature, whereas those of the dianions [{Mo(NO){HB(dmpz)₃}Cl}₂Q]²⁻ where Q = 1,4-OC₆H₄O, OC₆H₄EC₆H₄O (E = CO or S) and OC₆H₄CH=CHC₆H₄CH=CHC₆H₄O shows that the unpaired spins on each molybdenum centre are strongly correlated (J, the spin exchange integral A_Mo, the metal-hyperfine coupling constant). The electrochemical properties and the comproportionation constants for the reaction [{Mo(NO){HB(dmpz)₃} Cl}₂Q] + [{Mo(NO){HB(dmpz)₃}Cl}O]₂]²⁻2[{Mo(NO) {HB(dmpz)₃}Cl}₂Q]⁻ where Q = diphenolato bridge, are compared with related compounds containing benzenediamido and dianilido bridges.     

三个不同穿插的锌配合物的合成、结构和热动力学分析

使用醋酸锌,柔性的1,4-二甲基咪唑丁烷(bib)和三个刚性直链型羧酸混合配体,在溶剂热条件下合成了三个具有不同穿插结构的配合物。并通过元素分析,红外,X射线单晶衍射进行了表征。配合物 1是一个具有三种Z字链的四重穿插结构,配合物2是一个特殊的[2+2]型四重穿插结构,配合物3是一个具有双核结构单元的三重穿插结构。通过使用热重分析/微分热重和差示扫描量热(TG/DTG-DSC)技术研究了它们的热分解过程,由热重分析得出特殊的[2+2]型四重穿插结构稳定性最好,四重穿插结构比三重穿插结构稳定。使用Kissinger和Ozawa-Doyle法对配合物骨架坍塌过程进行了计算,得出配合物1-3的表观活化能分别为276.887、318.515、149.310 kJ·mol^-1,可以得出配合物1-3的反应速率关系为3 > 1 > 2。从热力学和动力学的角度来说明配合物的结构稳定性。其次,还对配合物1-3的荧光性质进行了表征。     

Degradation Method for Preparing Organo-Arsenic and-Antimony Polytungstates and Comparative Study of Corresponding Polymolybdates

In repeating and extending the syntheses of organo-arsenic polytungstates,we found that the "Degradation Method",taking sodium metatungstate as the starting material,was much more profita-ble.The known compound (CN3H6)5[(C6H5As)2W6O25H]2H2O(1) was read-ily reproduced with a high yield.A new compound (CN3H6)6[(p-OH,m-NO2C6H3As)2W6O25](2) was likewise synthesized.This "Degradation Method" using the reaction of sodium metatungstate with organo-anti-monate led to the isolation of four compounds with definite composition although amorphous in appearance.The preparations of organo-arsenic polymolybdates and organo-antimony polymolybdates were also studied and six new organo-arsenic polymolybdates were isolated: (CN3H6)5[(C6H5As)2MoO25H]H2O(3),(CN3H6)4[(n-C3H7As)2Mo5O21]2H O (4),(CNH)4[(n-C3H7As)2Mo6O24](5),Cs2[(CH3)2AsMo4O15H](6),相似文献