【作者】 李会端；

【导师】 刘云凌； 庞广生；

【作者基本信息】 吉林大学 ， 无机化学， 2011， 博士

【摘要】 磷基酸盐化合物家族成员丰富,包括金属磷酸盐,亚磷酸盐,金属有机膦酸盐及其它一些无机-有机杂化骨架的磷基酸盐化合物。磷基酸盐化合物因其丰富的骨架组成、拓扑学结构的多样性,以及在光、电、磁、半导体、生物传感、医疗诊断、催化、吸附分离等领域的潜在应用,近些年来受到广泛关注。使用亚磷酸取代磷酸合成的金属亚磷酸盐化合物是磷基酸盐化合物家族中的一个重要成员。目前文献中已报道了大量涉及过渡,主族和稀土金属的亚磷酸盐化合物。相对于金属磷酸盐化合物,金属亚磷酸盐化合物同时具有金属阳离子配位状态的变化和和阴离子结构变化两方面可导致骨架结构多样性的特点,因此设计合成具有化学组成丰富、骨架结构新颖的金属亚磷酸盐化合物拥有更广阔的发展空间。同时将具有刚性配位构型的草酸引入亚磷酸盐化合物的合成体系,合成出另一类新颖的无机-有机杂化的金属亚磷酸草酸盐微孔化合物,进一步丰富了磷基酸盐化合物家族的组成和结构化学。使用有机膦酸取代磷酸合成的金属有机膦酸化合物是磷基酸盐化合物家族中的新成员。这类化合物同时具有无机材料的高热稳定性和有机基团的可修饰性等优点,是一类新型的无机-有机杂化骨架的磷基酸盐化合物。伴随着合成研究的深入发展,其功能性研究也逐步引起人们的关注。定向设计和合成具有新颖结构的金属有机膦酸盐配位化合物并对其有机基团进行功能性修饰,为磷基酸盐化合物的合成带来新的研究热点。相对于文献中过渡金属亚磷酸盐化合物的大量合成报道,亚磷酸铟化合物的合成研究较少。本论文基于主族金属铟的亚磷酸盐和亚磷酸草酸盐化合物,过渡金属(Cd.Ni)的有机膦酸盐化合物的水热合成和结构表征为研究对象,主要完成了以下几方面的工作：(1)以有机膦酸NTP为配体,Cd为金属源,在水热条件下合成出两个具有三维结构有机膦酸镉微孔化合物Na|Cd2[N(CH2PO3H)(CH2PO3)2(H2O)](JCdP-1)和Na2|Cd5[N(CH2PO3)3]2(H2O)2|(JCdP-2)。不同的酸度条件下,NTP不同程度的去质子化,与Cd2+离子螯合配位产生不同的次级结构单元,进而构筑出完全不同的两种结构。JCdP-1是在pH接近7的中性条件下合成出来的,它的结构是由Cd2+阳离子与阴离子骨架的NTP配体通过共价键和氢键作用构筑而成的三维配位骨架结构,Na+离子存在于骨架间隙平衡骨架的负电荷。在化合物JCdP-1的配位骨架中,每个阴离子骨架的配体NTP采用μ7的配位模式,首先与两个镉原子进行螯合配位,形成一个新颖的次级结构单元Cd2(NTP)；再通过CP03与相邻的五个镉原子桥连配位,形成JCdP-1的三维配位网络结构。JCdP-2是在pH=8的弱碱性条件下合成出来的,它的结构由Cd2+阳离子与阴离子骨架的NTP配体通过共价键和氢键作用构筑而成的三维配位骨架结构。在化合物JCdP-2的配位骨架中,每个阴离子骨架的配体采用μ8的配位模式,与三个镉原子螯合进行配位,构筑成另一个新颖的次级结构单元Cd3(NTP)；再通过CPO3与相邻的五个镉原子桥连配位,形成JCdP-2的骨架结构。在z轴方向存在一维孔道,Na+离子存在于骨架间隙来平衡骨架的负电荷。(2)以有机膦酸N-膦酰甲基-(L)-脯胺酸为配体,在水热条件下合成一个层状结构的有机膦酸镍化合物|H2O|[Ni3(O3PCH2-NC4H7-CO2)2(H2O)4](JNiP-3)。JNiP-3的结构是由Ni06,Ni05(N)和CP03通过共边或共顶点交替连接构筑成的二维层状结构,配体结构中的五员环(环戊基)指向层与层之间,沿c轴方向存在十二员环孔道。磁性研究结果表明,该化合物表现出顺磁性。(3)将草酸引入亚磷酸铟化合物的合成体系,在In(NO3)3-H3PO3-H2C2O4-organic amine的水热体系中成功合成出两个拓扑学结构不同的无机-有机杂化的亚磷酸草酸铟开放骨架化合物|C6H14N2|[In2(HPO3)3(C2O4)](JInP-4)和|C4H12N2|[In2(HPO3)3(C2O4)](JInP-5)JInP-4是以dabco为模板剂在水热条件下合成出来的,是由In06八面体、HP03假四面体、C204基团通过共顶点交替连接构筑成的具有三维开放骨架结构的化合物。在两个方向上同时存在穿插孔道,质子化的dabco分子存在于孔道中,与主体骨架之间存在着氢键相互作用。在JInP-4的结构中,C204仅仅参与了杂化层的构成并改变了杂化层的结构,正是由于C204的配位作用,使得In06的刚性配位结构发生扭曲,结构中沿c轴方向出现一对左右手对称的螺旋链。JInP-5是在水热条件下以哌嗪为模板剂合成出来的,它的三维骨架结构也是由InO6八面体,HP03假四面体和C204基团通过共顶点交替连接构筑而成的。首先是InO6和HP03共顶点交替连接构筑成四、八员环的网层,C204充当桥连配体,将其进一步连接成三维结构。结构中具有八、八、十二员环的多维穿插孔道,客体分子pip存在于孔道中。对在不同温度下处理的JInP-5的样品进行粉末XRD表征,研究结果表明化合物JInP-5的开放骨架结构随温度变化出现转晶。(4)在水热条件下,以铟为金属源,亚磷酸为反应原料,成功合成出两个具有三维开放骨架结构的亚磷酸铟|(C4H12N2)0.5(H3O)|[In4(H2O)3(HPO3)7] (JInP-6), |(C10H10N2)1.5(H3O)3|[In18(H2O)12(HPO4)12(HPO3)16(H2PO3)6](JInP-7)和一个层状结构亚磷酸铟|H3O|[In(HPO3)2](JInP-8)。研究结果表明随着有机模板剂尺寸的增大,起到了一定支撑孔道的作用。JInP-6是在以pip为模板剂的水热条件下合成的。首先In06或In05(H20)八面体,HPO3假四面体交替连接构形成具有四、六、十二员环窗口的二维层,二维层之间以AB的顺序沿z轴方向堆积排列,再通过In(2)O6八面体的柱支撑进一步连接成化合物JInP-6的开放骨架结构,在[100]和[010]方向上分别具有十二员环孔道,质子化的哌嗪和水分子等客体分子填充在孔道中。JInP-7是在以4,4’-bipy为模板剂的水热条件下合成的。具有与JInP-6结构中相同的二维层,另外,两个In(2)O6八面体与三个HP(4)03假四面体共顶点交替连接形成一个五聚体的柱,将上述的以AA方式堆积的层状结构沿z轴方向支撑起来形成化合物JInP-7的三维骨架结构,在[110]和[010]方向上分别具有十六员环孔道,质子化4,4’-bipy和水等客体分子填充在孔道中。JInP-8是在氟离子存在的水热条件下以pip为模板剂的合成出来的。首先,In06八面体和HP03假四面体共顶点交替连接形成6*1的次级结构单元,次级结构单元之间再通过共边连接的方式形成JInP-8结构中的层,质子化水分子位于层间。该化合物是具有(3,6)-双节点的kagome dual (kgd)拓扑网络结构,顶点符号为(43)2(46)。更多还原

【Abstract】 The family of metal phosphorus-based microporous compounds has a rich composition, including metal phosphates and phosphites, metal organophosphonates and other inorganic-organic hybrid compounds. In recent years, metal phosphorus-based frameworks have been extensively researched due to their rich chemical composition, novel structural topology and potential application in the fields of optics, electricity, magnetism, bio-sensing, medical diagnostics, catalysis, adsorption and separation.Novel metal phosphites, an important family member of the metal phosphorus-based acid framework, have been synthesized by using phosphite as a substitute to phosphate. Recent literature reports metal phosphites synthesized from transition, main group and rare earth metal. As compared to metal phosphates, metal phosphites possess two characteristics which lead to a high level of structural diversity, the coordination mode of metal cations is varied and the structure of phosphate anion is changed. The rich chemical composition, novel topology and structure of metal phosphites, makes the design and synthesis of these materials a promising research area. Oxalate exhibits a rigid coordination geometry, it has been incorporated into the synthesis of metal phosphates, thus allowing the formation of novel inorganic-organic hybrid metal phosphite-oxalate frameworks. The successful synthesis of metal phosphite-oxalate has enriched the structural chemistry of metal phosphorus-based acid frameworks.Novel metal organophosphonates were hydrothermally prepared by using organic phosphonic acid as a substitute for phosphate. Inorganic-organic hybrid frameworks of metal organophosphonates are a new member of the metal phosphorus-based microporous family of compounds. This new class of materials possesses the following two advantages:high thermal stability and ease of structural modification through modification of organic moieties. The development of synthesis of organophosphates has been well studied and greater emphasis is now placed on rational design as well as studying and improving the functionality of these materials.There is limited literature on indium phosphite compounds as compared to the large number of reports of transition metal phosphite. This work is focuses on the synthesis and structure characterization of novel indium phosphite, indium phosphite-oxalate as well as metal organophosphonates involving cadmium and nickel. The primary research results are listed as follows:(1) Reactions of NTP with Cd(oac)2 under hydro thermal conditions afforded two novel 3D cadmium organophosphonate compounds Na|Cd2 [N(CH2PO3H)(CH2PO3)2(H2O)](JCdP-1) and Na2|Cd5[N(CH2PO3)3]2(H2O)2| (JCdP-2). NTP was gradually deprotonated under different acidity conditions and chelated with Cd2+ to produce different secondary building units (SBU), these SBUs combined and constructed the novel structures of JCdP-1 and JCdP-2.JCdP-1 was synthesized under neutral condition with a pH value close to 7. Its framework is constructed from cadmium cations and NTP anionic ligands connected through covalent and hydrogen bonds. Sodium cations are in the free volume to balance the negative charges from the framework. In the coordinated network of JCdP-1, each anionic NTP adopts aμ7 coordinated model, chelating with two cadmium cations to form a new secondary building units SBU-1, formulated as Cd2(NTP) and bridging with other five cadmium cations through CPO3, resulting in the 3D coordinated network structure of JCdP-1.JCdP-2 was synthesized under weak condition with a pH value close to 8. Its framework is constructed from cadmium cations and NTP anionic ligands connected through covalent and hydrogen bonds. In the coordinated network of JCdP-2, each anionic NTP adopts aμ8 coordinated model, chelating with three cadmium cations to form another new secondary building units SBU-2, formulated as Cd3(NTP). SBU-2 is bridged with five other cadmium cations through CPO3, resulting in the 3D coordinated network structure of JCdP-2. There exists a one-dimensional channel along z axis and sodium cations are in the channels to balance the negative charges from the framework.(2) A novel 2D layer structure of|H2O|[Ni3(O3PCH2-NC4H7-CO2)2(H2O)4](JNiP-3) was hydrothermally prepared by using A/-(phosphonomethyl)proline (H3L) as a ligand. The structure of JNiP-3 is constructed from alternating vertex-sharing or edge-sharing NiO6 (or NiO5N) octahedra and O3PC tetrahedral. The cyclopentyl moiety of H3L is grafted onto the layer through coordination of CPO3, CO2 and (CH2)2NCH2 with central nickel atoms and directed into the interlayer spaces. There exists a one-dimensional rhombohedra 12-MRs channel in the [001] direction, water guest molecules are located in the channels. Magnetic studies show that JNiP-3 exhibits a paramagnetic behavior.(3) Oxalate was incorporated into the synthesis system of indium phosphite and two novel indium phosphite-oxalate compounds |C4H12N2|[In2(HPO3)3(C2O4)] (JInP-4) and|C6H14N2|[In2(HPO3)3(C2O4)] (JInP-5) were prepared in the hydrothermal system of In(NO3)3·4H2O-H3PO3-H2C2O4-organic amine. The two hybrid frameworks obtained possess different framework topologies.JInP-4 was hydrothermally synthesized using dabco as an organic templating agent. Its 3D open-framework structure is constructed from vertex-sharing InO6 octahedra, HPO3 pseudo-pyramidal and C2O4 groups. The assembly of these building units generates intersecting channels along two different directions. Contained within the channels are protonated dabco molecules, which interact with the host framework through hydrogen bonding. In the structure of JInP-4, the oxalate groups are incorporated into the indium phosphite layer thus changing the structure of the hybrid layer. The chelating coordination of the oxalate with indium, InO6 has distorted octahedral geometry. Another structural feature of JInP-4 is the presence of left-handed and right-handed helical chains.In the presence of piperazine as an organic template agent, JInP-5 was prepared under hydrothermal conditions. Its 3D open-framework structure is constructed from alternating vertex-sharing InO6 octahedra, HPO3 pseudo-pyramidal and C2O4 groups. Firstly, InO6 octahedra and HPO3 pseudo-pyramidal are linked alternatively to form a 4,8-ring 2D layer. These 2D layers stacked in an AB sequence with oxalate groups acting as a bridging ligand thus forming the novel 3D hybrid framework. There existed 8,8, and 12-ring multi-dimensional intersecting channels, which contain protonated piperazine molecule. The phase transformation of JInP-5 was also investigated.(4) In the presence of different organic amine as template, two novel 3D open-framework structure of indium phosphite|(C4H12N2)0.5(H3O) [In4(H2O)3(HPO3)7](JInP-6),|(C10H10N2)1.5(H30)3|[In18(H2(HPO3)16 (H2PO3)6](JInP-7) and a novel layered structure of indium phosphate |H3O|[In(HPO3)2](JInP-8) were successfully synthesized under hydro thermal conditions. The investigations revealed that:an increase in the size of the organic template resulted in compounds featuring large channels.JInP-6 was hydrothermally synthesized by using piperizine as a template. Its structure can be described as follows:Firstly, InO6 (or InO5H2O)) octahedra, HPO3 pseudo-pyramidal linked alternatively to form a layer structure with 4,6, and 12-ring windows. These layers are stacked in an AB sequence along the z axis and further connected by InO6 octahedra forming the 3D structure of JInP-6. There are 12-ring intersecting channels along [100] and [010] direction, which contain protonated piperazine and water molecules.Using 4,4’-bipy as an organic templating agent, JInP-7 was prepared under hydrothermal conditions. JInP-7 has the same layer structure as in the structure of JInP-6, two InO6 octahedra and three HPO3 pseudo-pyramidal shared their vertex to from a pentamer, which acts as a pillar connecting these layers into the novel 3D structure of JInP-7. Present are intersecting 16-ring channels along [110] and [010] direction, in which protonated 4,4’-bipy and water molecules were located.In the presence of fluoride ions, JInP-8 was synthesized under hydrothermal conditions. Its 2D layer structure can be described as follows:InO6 octahedra and HPO3 pseudo-pyramidal linked alternatively into a novel secondary building unit (SBU),6*1, these SBUs are further connected through edge-sharing into the layer structure of JInP-8, protonated water molecules are located in the interlayer spaces. From a topological perspective, JInP-8 exhibits a (3,6)-connected layer structure with kgd (kagome dual) topology with a vertex symbol (43)2(46).更多还原