新型层状晶态聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵有机聚合物-无机杂化材料的合成与表征

将苯乙烯-苯乙烯基膦酸共聚物、 二水合醋酸锌和磷酸二氢铵在温和的条件下反应, 通过调节无机磷酸盐和有机膦酸的比例, 合成了一系列有机聚合物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵. 通过FTIR, TG, XRD, SEM和TEM等手段对其进行表征并测试了其催化性能. 结果表明, 聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵是一种新型层状晶态的有机聚合物-无机杂化材料, 具有较高的热稳定性和特殊的多孔结构. 将其作为催化剂载体, 以芳香二胺作为连接基团, 轴向固载手性Salen Mn(Ⅲ)制备了多相催化剂, 并用于非功能化烯烃的不对称环氧化反应. 催化实验结果表明, 该催化剂在以m-CPBA/NMO为氧化体系催化α-甲基苯乙烯和茚的反应中显示出优良的催化性能, 如催化茚的e.e.值可达99%, 并且可以回收利用, 循环使用8次仍具有较好的催化活性, 具有潜在的工业应用价值.     

新型烷氧基修饰的手性SalenMn（Ⅲ）固载催化剂的合成及其在非功能化烯烃不对称环氧化反应中的应用

合成了一系列以有机聚合物-无机杂化材料聚（苯乙烯-苯乙烯基膦酸）-磷酸氢锆（ZPS-PVPA）为载体,烷氧基为连接基团的新型固载手性Salen Mn（III）催化剂,并运用FT-IR,UV-vis,XPS,SEM,TG,元素分析等手段对其进行了表征.以m-CPBA为氧化剂,茚和α-甲基苯乙烯为底物,考察了催化剂对非功能...     

新型晶态层状载体聚(苯乙烯-苯乙烯基膦酸)-磷酸锌轴向固载手性Salen Mn(Ⅲ)的合成及催化烯烃的环氧化性能

在温和条件合成了新型晶态层状有机聚合物-无机杂化载体材料聚(苯乙烯-苯乙烯基膦酸)-磷酸锌, 结合实验数据提出了其可能的理想结构模型. 对该载体进行氯甲基化和酚羟基化修饰后, 轴向配位固载手性Salen Mn(Ⅲ), 合成了一类新型的多相催化剂. 以间氯过氧苯甲酸为氧源, 考察了其对α-甲基苯乙烯及茚不对称环氧化反应的催化性能. 结果表明, 这类固载催化剂具有与均相Jacobsen催化剂相当或更高的催化活性和对映选择性, 并具有优良的重复使用性. 特别是在该氧化体系中, 当无助催化剂N-甲基吗啉氮氧化物(NMO)参与时, 固载催化剂获得更高的转化率及e.e.值, 这为其扩大化生产增加了可能性.     

Cd基化合物纳米晶-有机聚合物杂化太阳能电池研究进展

有机-无机杂化太阳能电池因其结合了有机材料和无机材料各自的优势而引起了人们的广泛关注和研究. Cd基化合物纳米晶因其具有制备方法简单、尺寸及形貌可控、载流子迁移率高和稳定性好等优点而成为最早被研究的一类无机受体. 本文介绍了有机-无机杂化太阳能电池的结构及原理, 分析了影响有机-无机杂化太阳能电池效率的三个主要因素, 分别是开路电压(V_oc)、短路电流(J_sc)和填充因子(FF). 从改善Cd基化合物纳米晶的合成方法, 增加Cd基化合物纳米晶和有机聚合物间的界面接触, 以及优化Cd基化合物纳米晶和有机聚合物所用溶剂和所占比例等方面阐述了近年来Cd基化合物纳米晶-有机聚合物杂化太阳能电池的研究进展. 并展望了Cd基化合物纳米晶-有机聚合物杂化太阳能电池的发展方向.     

有机-无机杂化氧化硅基介孔材料

有机基团可以通过嫁接或共聚的方法引入到氧化硅基介孔材料的孔表面或材料的骨架中,形成表面结合型和桥键型两大类有机-无机杂化氧化硅基介孔材料.本文综述了有机-无机杂化氧化硅基介孔材料的最新研究进展,介绍了其合成方法、应用及潜在的应用领域,详细总结了目前已报道的有机-无机杂化氧化硅基介孔材料的种类,展望了桥键型有机-无机杂化氧化硅基介孔材料的发展及应用前景.     

有机-无机杂化载体-聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆-在烯烃环氧化反应中的应用

有机聚合物-无机杂化载体-聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆-轴向固载手性Salen Mn髥催化剂,将其应用于非官能烯烃的多相不对称环氧化反应。结果表明:在没有昂贵轴向添加剂参与下,产率与对映选择性均急剧增加。以间氯过氧苯甲酸(m-CPBA)为氧化剂催化氧化α-methylstyrene,转化率从25.0%上升到98.8%;对映选择性从5.3%提高到67.3%。催化剂在循环使用5次以后,催化活性无明显改变。     

链接基团对固载手性Salen Mn(m)催化不对称环氧化反应的影响

制备了二胺和二酚修饰的晶态有机聚合物-无机杂化载体低聚苯乙烯基膦酸-膦酸氢锆(LCZSPP)轴向固载手性Salen Mn(Ⅲ)催化剂,将其应用于非官能烯烃的多相不对称环氧化反应.研究了两类轴向连接基团及助催化剂在催化不对称环氧化反应中的影响.结果表明,通过二胺为链接基团固载的催化剂在加入轴向助剂(NMO)的情况下,转化...     

酚氧基修饰的AlPS-PVPA固载手性Salen Mn(Ⅲ)催化剂的合成及催化烯烃不对称环氧化研究

以有机共聚物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸铝(AlPS-PVPA)为载体,酚氧基为连接基团,轴向配位手性salen Mn(Ⅲ)制备了新型固载手性salen Mn(Ⅲ)催化剂,并运用FT-IR,UV-vis,XPS,SEM,TG,元素分析等手段对其进行了表征.以m-CPBA为氧化剂,茚和α-甲基苯乙烯为底物,考察了催化剂对非功能化烯烃不对称环氧化反应的催化性能.结果表明,在相同的条件下,固载催化剂3a~3d在不加助催化剂NMO时显示出了优良的催化活性,其转化率和ee值均比添加了轴向配体NMO时有很大的提高(ee%,99.2 vs.45.9;conv%,98.6 vs.64.6),这种现象与大多数文献报道相反.此外,催化剂容易分离,且回收使用9次仍能保持较好的催化活性.     

正丁胺对晶态层状苯乙烯基膦酸-磷酸氢锆的插层研究

合成了晶态层状有机-无机多功能材料苯乙烯基膦酸-磷酸氢锆(α-ZPPVPA),并研究了正丁胺(BA)对α-ZPPVPA的插层性能。用元素分析、XRD、IR、TG、SEM和TEM等分析方法对α-ZPPVPA及其插层化合物α-ZPPVPA-BA进行了结构表征和形貌分析。结果表明,正丁胺成功地插入了α-ZPPVPA层板之间,层间距为2.41 nm,正丁胺的插入使α-ZPPVPA的层间距(1.66 nm)增大了0.75 nm,插入的正丁胺在α-ZPPVPA中呈双分子层排列,且苯乙烯基侧链不饱和双键的存在不影响α-ZPPVPA与正丁胺的插层反应。     

生物可降解聚膦腈材料的功能化及研究进展

聚膦腈是一类主链由磷氮原子交替组成,每个磷原子带有两个有机官能团侧基的有机-无机杂化高分子,其化学结构强大的可设计性赋予了材料丰富的理化性能。作为生物学用途的聚膦腈材料,生物相容性、生物可降解性和功能化改性是实现其应用的关键因素。本文从数种功能化聚膦腈(如光致荧光、导电、聚膦腈-聚酯共聚物)的制备、聚膦腈的降解机理和降解行为调控,以及生物可降解聚膦腈作为组织工程支架材料、药物载体材料和基因转染材料等几个方面,较为全面地综述了聚膦腈生物医用高分子的研究进展。     

Porous Zirconium–Phytic Acid Hybrid: a Highly Efficient Catalyst for Meerwein–Ponndorf–Verley Reductions

The utilization of compounds from natural sources to prepare functional materials is of great importance. Herein, we describe for the first time the preparation of organic–inorganic hybrid catalysts by using natural phytic acid as building block. Zirconium phosphonate (Zr‐PhyA) was synthesized by reaction of phytic acid and ZrCl₄ and was obtained as a mesoporous material with pore sizes centered around 8.5 nm. Zr‐PhyA was used to catalyze the mild and selective Meerwein–Ponndorf–Verley (MPV) reduction of various carbonyl compounds, e.g., of levulinic acid and its esters into γ‐valerolactone. Further studies indicated that both Zr and phosphate groups contribute significantly to the excellent performance of Zr‐PhyA.     

Water‐Mediated Proton Conduction in a Robust Triazolyl Phosphonate Metal–Organic Framework with Hydrophilic Nanochannels

The development of water‐mediated proton‐conducting materials operating above 100 °C remains challenging because the extended structures of existing materials usually deteriorate at high temperatures. A new triazolyl phosphonate metal–organic framework (MOF) [La₃ L ₄(H₂O)₆]Cl ? x H₂O ( 1 , L ^2?=4‐(4H‐1,2,4‐triazol‐4‐yl)phenyl phosphonate) with highly hydrophilic 1D channels was synthesized hydrothermally. Compound 1 is an example of a phosphonate MOF with large regular pores with 1.9 nm in diameter. It forms a water‐stable, porous structure that can be reversibly hydrated and dehydrated. The proton‐conducting properties of 1 were investigated by impedance spectroscopy. Magic‐angle spinning (MAS) and pulse field gradient (PFG) NMR spectroscopies confirm the dynamic nature of the incorporated water molecules. The diffusivities, determined by PFG NMR and IR microscopy, were found to be close to that of liquid water. This porous framework accomplishes the challenges of water stability and proton conduction even at 110 °C. The conductivity in 1 is proposed to occur by the vehicle mechanism.     

On phosphorus chemical shift anisotropy in metal (IV) phosphates and phosphonates: A 31P NMR experimental study

The phosphorus chemical shift anisotropies, ³¹PΔcs, and asymmetry parameters η were measured by the ³¹P{¹H} NMR experiments in static and low-frequency spinning samples of the zirconium phosphates and phosphonates and also in the mixed Zr (IV)/Sn (IV) phosphate/phosphonate material. The data obtained have shown a 111 connectivity in the HPO₄ and PO₃ groups, which does not change at modification and intercalation of the materials. The ³¹PΔcs values of the phosphonate groups (43–49 ppm) significantly surpass the values characterizing the HPO₄ groups (23–37 ppm). The ³¹P Δcs values obtained for the metal (IV) phosphates were discussed in terms of P-O distances. The ³¹P chemical shift anisotropy parameters can help at elucidation of local structures in phosphate and phosphonate materials.     

Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection

Rational selection and modification of rare earth metal centers and photoactive organic linkers enables designable multiphotofunctionality to come to fruition in new hybrid coordination polymer materials. By using a viologen‐functionalized diphosphonate linker, two terbium phosphonate compounds ( Tb‐1 and Tb‐2 ) have been constructed, which display reversible photochromic reactions in response to UV light and soft X‐ray irradiation. In addition, the photo‐induced electron‐transfer reaction can modulate the luminescent emission to thus realize photoluminescence switching behavior. Furthermore, both terbium phosphonates can serve as highly sensitive sensors to probe Cu²⁺ in solution through their luminescence. Thus, they represent the first photochromic examples of lanthanide phosphonate‐based materials with photomodulated luminescence and sensitive detection of metal ions.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Novel phosphate–phosphonate hybrid nanomaterials applied to biology

A new process for preparing oligonucleotide arrays is described that uses surface grafting chemistry which is fundamentally different from the electrostatic adsorption and organic covalent binding methods normally employed. Solid supports are modified with a mixed organic/inorganic zirconium phosphonate monolayer film providing a stable, well-defined interface. Oligonucleotide probes terminated with phosphate are spotted directly to the zirconated surface forming a covalent linkage. Specific binding of terminal phosphate groups with minimal binding of the internal phosphate diesters has been demonstrated. On the other hand, the reaction of a bisphosphonate bone resorption inhibitor (Zoledronate) with calcium deficient apatites (CDAs) was studied as a potential route to local drug delivery systems active against bone resorption disorders. A simple mathematical model of the Zoledronate/CDA interaction was designed that correctly described the adsorption of Zoledronate onto CDAs. The resulting Zoledronate-loaded materials were found to release the drug in different phosphate-containing media, with a satisfactory agreement between experimental data and the values predicted from the model.     

Syntheses, characterizations, and single-crystal X-ray structures of soluble titanium alkoxide phosphonates

Reactions of Ti(OiPr)4 with different phosphonic acids RPO3H2 (R = Ph, 4-CNPh, Me, tBu) in organic solvents have been investigated. In the presence of small amounts of water, the new molecular titanium oxide alkoxide phosphonates [Ti4(mu 3-O)(OiPr)5(mu-OiPr)3(RPO3)3].DMSO [R = Ph (1), Me (2), tBu (3), 4-CNPh (4)] were isolated. The single-crystal X-ray structure analyses of 1 and 2 revealed hexacoordinated titanium atoms and a connectivity of (111) for each phosphonate. Under rigorous exclusion of water, the reaction of Ti(OiPr)4 with tert-butylphosphonic acid in toluene gave the titanium phosphonate tetramer [Ti(OiPr)2(tBuPO3)]4 (5). A single-crystal X-ray structure analysis of 5 revealed a 5 + 1 coordination of the titanium atoms as a result of the (112) connectivity of each phosphonate; such a coordination mode has never been reported for a titanium phosphate, phosphonate, or phosphinate. Compounds 1-5 were characterized by FT-IR, 31P MAS NMR, and solution multinuclear NMR (1H, 13C(1H,) 31P(1H)) spectroscopies. 13C CP MAS NMR experiments were carried out on arylphosphonates 1 and 4. Solution NMR experiments were also used to investigate the exchange reaction between 1 and 2 and the conversion of 5 to [Ti4(mu 3-O)(OiPr)5(mu-OiPr)3(tBuPO3)3].iPrOH by partial hydrolysis in the presence of Ti(OiPr)4. The phosphonate clusters 1-5 are soluble in organic solvents and are likely intermediates in the sol-gel processing of inorganic-organic hybrids based on titanium oxide and phosphonate groups that we are currently developing.     

Porous Organic Zirconium Phosphonate as Efficient Catalysts for the Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ‐Valerolactone without External Hydrogen

Organic hybrid zirconium phosphonate materials (ZrATMP, ZrEDTMPS, ZrDTPMPA, and ZrHEDP) were synthesized through reaction of organic phosphonic acid sodium salt and ZrOCl₂ in water, which exhibited high catalytic activity on the conversion of ethyl levulinate (EL) to γ‐valerolactone (GVL) in the presence of isopropanol. The obtained catalysts were characterized by FT‐IR, TGA, XRD, BET, XPS, ICP‐AES, SEM, TEM, NH₃‐TPD, and CO₂‐TPD. The results demonstrate that the number of acid sites and basic sites between the layers of the catalysts play a very important role in promoting the conversion of EL to GVL and that the functional groups that exist in phosphates could regulate the number of acid and basic sites. Meanwhile, the catalysts could be easily separated from the reaction system and reused at least five times without any obvious decrease in activity or selectivity.     

Assembly of two novel inorganic–organic hybrid solids based on 3-(aminomethyl)pyridine ligand

Two new inorganic–organic hybrids, (Hampy)Zn₂(PO₄) (HPO₃) (1) and (ampy)Zn₂(HPO₃)₂ (2), where ampy = 3-(aminomethyl)pyridine, have been solvothermally prepared and structurally characterized. Compound 1 exhibits an unusual two-dimensional layer structure, which possesses a central 4.8² zincophosphate sheet wrapped by infinite zincophosphite chains. Left- and right-handed helical chains participate in the formation of the zincophosphate layer. Compound 2 features a three-dimensional pillared-layer structure, in which two-dimensional Zn^II(HPO₃) inorganic sheets were cross-linked by ampy ligands. The simultaneous occurrence of zinc-amine helical chains in 2 is unique and, to the best of our knowledge, firstly encountered in phosphite/phosphate hybrid materials. Different coordination modes and roles of the same ampy ligand were observed in the formation of the hybrid structures.