基于有机改性硅氧烷作为连接体组装稀土光功能杂化材料

针对近年来基于有机改性硅氧烷作为连接体构筑的光功能稀土杂化材料的最新进展进行了评述,其重点着眼于稀土离子的优良光敏化有机配体修饰硅氧烷偶联剂获得有机改性硅氧烷,以其作为多功能连接体(分子桥)来实现对发光稀土杂化材料体系的化学键组装。内容主要涉及基于芳香羧酸衍生物类改性硅氧烷构筑稀土杂化材料、基于β-二酮及类β-二酮衍生物类改性硅氧烷构筑稀土杂化材料、基于大环配体衍生物类改性硅氧烷构筑稀土杂化材料、基于杂环等衍生物类改性硅氧烷构筑稀土杂化材料、基于有机改性硅氧烷多元组装稀土杂化材料及基于离子液体改性硅氧烷构筑稀土介孔硅杂化材料几个重要方面。主要结合我们自己的近期研究工作,通过系统总结来展现该领域的研究面貌并提出未来展望。     

稀土配合物杂化发光材料的组装及光物理性质研究进展

稀土配合物兼具无机物稳定性好以及有机物荧光量子效率高的优点,而且具有可设计性,制备简便,容易修饰,荧光性质优异（发射谱带窄、色纯度高、荧光寿命长、量子产率高以及发射光谱范围覆盖可见和近红外光区等）．但配合物的光、热、化学稳定性和机械加工性能相对较差,因而限制了其在很多领域中的实际应用．近年来的研究表明,将稀土配合物引入到各种基质材料中可以改善其稳定性及机械加工性能,并对其光物理性质产生调制作用．根据基质材料的不同,杂化材料可分为无机基质、无机／有机复合基质及有机基质杂化材料．本文综述了这些不同基质稀土配合物杂化发光材料的研究进展,探讨了主客体间相互作用对杂化材料光物理性质及稳定性的影响,为实现稀土配合物杂化发光材料在光学器件领域（LED照明、光纤维、光学放大器及激光等）及生命分析领域的应用提供了重要的理论依据．     

聚合物纳米杂化高性能光功能材料

近年来材料科学与技术的不断发展,对光学材料提出了高性能化和多功能化的需求,为此,研究者们结合传统有机聚合物光学材料和无机光学材料的优势,提出了备受关注的聚合物纳米粒子杂化的策略.本文首先概述了针对杂化材料透光性进行控制的杂化方法,指出杂化方法的选择很大程度上与材料性质尤其是纳米相的性质相关,而杂化方法的目的则在于实现纳米杂化材料的透光性控制,纳米杂化光功能材料实现功能的前提即为透光性.随后,分别介绍了聚合物纳米杂化策略在高折射率材料与发光材料中的应用.对于高折射率材料,总结了提升材料折射率的不同策略.对于发光材料,总结了基于聚合物相和纳米相之间不同的相互作用而采用各种杂化方式以及相关的性能提升.接下来,讨论了聚合物纳米杂化光功能材料在光学和机械、热学、表面性能方面的调控手段和性能提升的策略.最后,提出了下一代光学杂化材料所面临的困难与挑战,以进一步推动这一领域的发展.     

溶胶-凝胶法合成有机/无机杂化材料进展——1.组分间以化学键作用的有机/无机杂化材料

介绍了溶胶－凝胶法（Sol-gel process)制备组分间以化学键作用的有机／无机杂化材料的基本情况,根据合成方法进行分类,并指出其发展趋势。     

层状稀土氢氧化物杂化发光材料研究进展

层状稀土氢氧化物(LRHs)是一类具有二维层状结构的新型无机层状功能材料.由于LRHs具有可变的组成、丰富的插层化学行为以及稀土离子特有的荧光性质等优点,因此是一种很有发展潜力的新型发光功能材料.本文综述了层状稀土氢氧化物杂化发光材料的研究进展,探讨了主客体间相互作用对其光物理性质及稳定性的影响,为实现层状稀土氢氧化物杂化发光材料在光学器件领域(LED照明和光纤维等)及生命分析领域的应用提供了重要的理论依据.     

聚合物纳米杂化材料的控制合成、自组装及功能化

聚合物纳米杂化材料的制备及功能化是当前国际前沿研究课题之一.特殊结构的聚合物可以通过分子间特殊相互作用,在纳米尺度上自发地组装成具有特殊结构和形态的集合体,这类材料在新材料、电子以及生物医学等领域具有广泛的应用前景.本文介绍国内外,特别是厦门大学在双亲性分子及嵌段共聚物的模板自组装、基于POSS单体纳米构筑单元以及POSS嵌段聚合物自组装的有机/无机纳米杂化材料、模板控制导电高分子材料纳米形态构筑等领域材料的可控合成和组装,与此同时对相关材料的性能及功能化应用进行了简要的讨论.     

多酸-有机聚合物超分子自组装杂化材料

多酸具有多样的拓扑结构和优异的理化性质,在催化、光电材料和药物等领域显示出广阔的应用前景。多酸-有机聚合物超分子自组装杂化材料不仅有效融合了多酸丰富的功能特性和有机聚合物良好的加工性,而且其有序的自组装结构还赋予材料更多优异的功能调控性。静电复合、氢键作用、共价键连等超分子策略是将多酸引入到聚合物基质中的有效方法。本文总结了多酸-有机聚合物超分子杂化材料近几年的最新研究进展,重点介绍了这类杂化材料的构筑策略、其有序的自组装行为以及超分子功能特性的调控等。     

多金属氧酸盐簇-聚合物杂化功能材料的研究进展

随着高新科技的快速发展与日益更替,兼有无机材料多功能性和聚合物可加工性的杂化材料具有重要的应用前景。本文论述并回顾了将多金属氧酸盐簇(Polyoxometalates)与聚合物通过共价键连接制备多金属氧酸盐簇-聚合物杂化物(Polyoxometalate-Polymer Hybrids)的研究现状。依据所制备杂化物中聚合物链的构型进行分类,综述了近年来该领域的研究进展,并重点介绍了本课题组在过去几年里的研究成果。     

有机-无机杂化分离膜研究进展

有机-无机杂化膜材料结合了有机膜材料和无机膜材料的优良性能,已成为分离膜材料研究的一个热点。本文以有机、无机组分间相互作用类型对其进行分类,着重介绍组分间以化学键相结合的有机-无机杂化膜的优良特性,总结了影响此类杂化膜结构和性能的主要因素,概括了它在膜分离中的应用,提出了目前研究工作中存在的不足,并做出了简要的述评。     

Covalently bonded assembly and photoluminescent properties of rare earth/silica/poly(methyl methacrylate-co-maleic anhydride) hybrid materials

Copolymer (MMA-co-MAL) of methyl methacrylate (MMA) and maleic anhydride (MAL) was prepared and grafted by 3-aminopropyltriethoxysilane (APES), which behaves as the structural precursor for functional bridge to assemble the covalently bonded systems through the coordination to rare earth ions (Eu³⁺, Tb³⁺) with carboxylic groups of maleic anhydride. On the other hand, 1,10-phenanthroline (phen) is engaged in a second functional ligand to sensitize the luminescence of RE³⁺ (rare earth ions) by intramolecular energy transfer process. Meanwhile, the cohydrolysis and copolycondensation processes happened between triethoxysilyl of modified copolymer (MMA-co-MAL-APES) and tetraethoxysilane (TEOS) with Si–O covalent bonds, resulting in the polymer-inorganic hybrids (phen-RE-MMA MMA-co-MAL-Si) exhibiting characteristic red or green emissions of Eu or Tb ions. Especially the luminescent quantum efficiencies of europium hybrid systems are estimated and discussed in detail.     

Coordination bonding assembly and photophysical properties of Europium organic/inorganic/polymeric hybrid materials

Ternary organic/inorganic/polymeric hybrid material PVP-Eu-(DBM-Si)₃ (DBM = dibenzoylmethane; PVP = poly(4-vinylpyridine)) have been synthesized through the coordination bonds. The precursor DBM-Si is obtained by the modification of DBM molecule with a cross-linking reagent TEPIC (3-(triethoxysilyl)-propyl isocyanate), which is used to form the inorganic Si–O–Si networks with TEOS (tetraethoxysilane) after a hydrolysis and polycondensation process. PVP, which is obtained through the polymerization reaction using 4-vinylpyridine as the monomer in the presence of BPO (benzoyl peroxide), is used to form the organic polymeric C–C chains. For comparison, the binary organic/inorganic hybrid material Eu-(DBM-Si)₃ was also synthesized simultaneously. FT-IR (Fourier-transform infrared spectra), UV (ultraviolet absorption spectra), UV-DR (ultraviolet–visible diffuse reflection absorption spectra), SEM (scanning electron micrograph), PL (photoluminescence spectroscopy) and LDT (luminescence decay time) measurements are used to investigate the physical properties of the obtained hybrid materials. The results reveal that the ternary hybrids presents more regular morphology, higher red/orange ratio, stronger luminescent intensity, higher ⁵D₀ luminescence quantum efficiency and longer lifetime than the binary one, suggesting the property of the overall hybrid system is improved with the introduction of the organic polymer PVP.     

掺杂稀土配合物的无机/高分子纳米杂化薄膜的 制备与发光性能

通过在溶胶-凝胶过程中引入高分子组分,并将稀土配合物掺杂其中的方法得到了具有良好发光性能的无机/高分子杂化薄膜,它们有很好的韧性和透明性,测定了薄膜的荧光光谱和荧光寿命,发现它们均发射出稀土离子的特征荧光且寿命比本体配合物增长。透射电镜的观察表明配合物在SiO~2/高分子互穿网络中分布较均匀,分散尺度在20～30nm之间。     

Chemically bonded assembly and photophysical properties of luminescent hybrid polymeric materials embedded into silicon–oxygen network and carbon unit

Through the reaction between the hydroxyl groups of 2-hydroxyl-3-methylbenzoic acid (HMBA), the glycol (G), the diglycol (DG) or the polyethylene glycol (PEG) and the isocyanate groups of 3-(triethoxysilyl)-propyl isocyanate (TEPIC), the hybrid precursors HMBA-Si, G-Si, DG-Si and PEG-Si were obtained. And then the precursors HMBA-Si and G-Si (DG-Si, PEG-Si) have coordinated to the rare earth ions with the carbonyl group of G-Si (DG-Si, PEG-Si) and the carboxyl group of HMBA-Si to form the hybrid materials HMBA-G-RE-Si (HMBA-DG-RE-Si, HMBA-PEG-RE-Si) through hydrolysis and copolycondensation with the tetraethoxysilane (TEOS) via sol–gel process. Subsequently, the NMR, FT-IR and ultraviolet absorption spectra have indicated that the effective precursors have been obtained successfully and the obtained materials possess the characteristic fluorescent properties, thermal stabilities and regular trunk with hole-like microstructures.     

Polyisobutylene containing organic/inorganic hybrid block copolymers and their crystalline behavior

Block copolymer comprising of polyisobutylene (PIB) soft segment and poly(3‐(3,5,7,9,11,13,15‐heptaisobutyl‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxane‐1‐yl)propyl methacrylate) (PMAPOSS) hard segment was synthesized by combination of living carbocationic and reversible addition‐fragmentation chain transfer (RAFT) polymerizations. Block copolymers were characterized by ¹H and ²⁹Si NMR spectroscopy, FT‐IR study, energy dispersive X‐ray spectroscopy (EDX), and gel permeation chromatography (GPC). The EDX, combined with scanning electron microscopy (SEM) was employed for determination of elemental composition. Thermal transition and degradation behaviors were confirmed by differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA), respectively. Although both the PIB and MAPOSS homopolymers are amorphous in nature, in their block copolymers the PMAPOSS domain showed crystalline behavior, as confirmed from wide‐angle X‐ray scattering (WAXS) technique, DSC studies and polarized optical microscopy (POM). Interestingly, crystalline melting temperatures (T_m) can be tuned by changing the PIB to PMAPOSS block length ratios. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1125–1133     

Lanthanide/zinc centered photoactive hybrids with functional sulfonamide linkage: Coordination bonding assembly,characterization and photophysical properties

In this paper, two novel kinds of organic–inorganic monomer, SUA-APEMS and SUA-APS, have been achieved by modifying 5-sulfosalicylic acid (SUA) with 3-aminopropyl-methyl-diethoxylsilane (APEMS) and 3-aminopropyl trimethoxysilane (APS). These two organic–inorganic monomers were used as multi-functional bridged components, which can coordinate to metal ions (Tb³⁺/Eu³⁺/Zn²⁺) with carbonyl groups, strongly absorb ultraviolet and effectively transfer energy to metal ions through their triplet excited state, as well as involve in the sol–gel process with inorganic host precursor tetraethoxysilane (TEOS), resulting two series of molecular hybrid materials (named as SUA-APEMS/APS-RE) with double chemical bond (RE(Zn)–O coordination bond and Si–O covalent bond). The effective intra-molecular energy transfer process gives rise to the characteristic emission of metal ions and the chemical bond make the hybrid materials owning better properties.     

含氮多齿配体构筑的无机-有机杂化材料及其光催化研究进展

综述了金属离子与多齿含氮配体构筑的无机-有机杂化材料,并概述了这些材料在光催化降解亚甲基蓝(MB)方面的研究进展.为此类材料在光催化降解染料方面的研究提供了理论和实验基础.