【作者】 王灯旭；

【导师】 冯圣玉；

【作者基本信息】 山东大学 ， 高分子化学与物理， 2011， 博士

【摘要】 硅原子上带有官能化基团的小分子有机硅化合物称为官能化硅烷,分为π型官能化硅烷和杂原子型官能化硅烷。硅原子具有空的3d轨道,赋予了有机硅化合物许多独特的性质。一方面,π型和杂原子型官能基团分别可以给出不定域电子和孤对电子,可作为给电子体与具有空轨道的金属中心离子通过配位自组装形成小分子配合物或配位聚合物。由于硅原子的特殊结构和电子性质,所形成的配位化合物与一般的金属络合物相比,具有许多新颖的结构和更好的光、电、磁等性能。另一方面,与传统的碳化合物相比,官能化硅烷本身具有合成方法简单、热稳定性高,光学纯度高等优点。因此,官能化硅烷及配合物在有机光电材料、化学传感器及生物传感器等领域得到广泛的应用。本文围绕氮杂环与羧酸官能化硅烷的合成、组装及性能研究展开了一系列的研究工作。1.合成了一系列以苯基为桥的官能化硅烷的前驱体——溴苯基硅烷,包括溴原子在硅原子对位产物(1～7),溴原子在硅原子间位产物(8～11)以及苯撑产物(13),通过红外光谱、1H核磁共振谱和13C核磁共振谱等手段表征了其结构。研究了不同反应路线对产物的影响,找到了合成溴苯基硅烷的最佳反应条件,即采用有机锂试剂方法,以无水乙醚做反应溶剂,-78℃为反应温度。2.以溴苯基硅烷为起始原料,通过Ullmann缩合反应合成了一系列以苯基为桥的咪唑官能化硅烷,包括二(4-(1-咪唑基)苯基)二甲基硅烷(L1)、三(4-(1-咪唑基)苯基)甲基硅烷(L2)、二(4-(1-咪唑基)苯基)二苯基硅烷(L3)、三(4-(1-咪唑基)苯基)苯基硅烷(L4)、[二(4-(1-咪唑基)苯基)](4-溴苯基)苯基硅烷(L5)和[三(4-(1-咪唑基)苯基)](4-溴苯基)硅烷(L6),通过红外光谱、1H核磁共振谱、13C核磁共振谱和高分辨质谱等手段表征了其结构。研究了几种反应体系对产物的影响,找到了两种合适的反应体系。进一步研究表明这些化合物均具有良好的热稳定性,在紫外到蓝光区域有强烈的荧光发射,并且具有大的HOMO-LUMO能量差(4.9585 eV到5.1879 eV),使得这些化合物可以作为蓝光发射材料或空穴传输材料应用于有机电致发光领域。化合物L1～L4与Ag(Ⅰ)相互作用表明,随着Ag(Ⅰ)浓度的增加,对Ag(Ⅰ)显示不同的荧光响应。3.以溴苯基硅烷为起始原料,通过Ullmann缩合反应合成了一系列以苯基为桥的氮杂环官能化硅烷,包括二(4一(1-吡唑基)苯基)二甲基硅烷(L8)、二(3一(1一吡唑基)苯基)二甲基硅烷(L9)、三(4-(1-吡唑基)苯基)甲基硅烷(L10)、二(4-(1-苯并咪唑)苯基)二甲基硅烷(L11)、二(3-(1-苯并咪唑)苯基)二甲基硅烷(L12)、二(4-(4-甲基一1一咪唑基)苯基)二甲基硅烷(L13)、(3一(1一咪唑基)苯基)三甲基硅烷(L14)、二(3-(1-咪唑基)苯基)二甲基硅烷(L15)、三(3一(1-咪唑基)苯基)甲基硅烷(L16)和二(4-(1-吡唑基)苯基)甲基乙烯基硅烷(L17),通过红外光谱、1H核磁共振谱、13C核磁共振谱和高分辨质谱等手段表征了其结构。研究表明这些化合物具有良好的热稳定性,在紫外到蓝光区域有发射峰,可以作为蓝光发射材料应用于有机电致发光领域。对不同氮杂环官能化硅烷光学性能的比较表明,引入较大的共轭体系,在同一个分子中引入多个官能团以及在硅原子的对位(以苯基为桥)引入官能团是提高官能化硅烷的荧光效率的有效途径。4.以一种半刚性咪唑官能化硅烷作为配体,二(4一(1-咪唑基)苯基)二甲基硅烷(L1)为基体构筑了五种新的配位聚合物,[Ag(L1)]0.5[Ag(L1)]2·2.5ClO4-5H2O (CP-1), Ag(L1)PF6·H2O (CP-2), MnCl2(L1)2 (CP-3), Cu(Ll)Br (CP-41和Cu(L1)Cl(CP-5),用单晶X-射线衍射表征了其结构。结果显示这些金属有机化合物均是以一维链为基础的结构,说明L1是一种很好的线型配体。化合物CP-1含有两类一维链,通过编织和穿插而得到一种三维多孔结构,沿着a轴和b轴含有两种不同尺寸和形状的孔洞,高氯酸根离子和水分子分别填充在孔洞中。该化合物具有选择性离子交换性能,可以与PF6-和BF4-离子交换,而不能与CF3SO3-交换。化合物CP-3是一种以金属大环为构建单元的一维链通过氢键相互作用形成的二维层状结构。化合物CP-4和CP-5均是一维弯折链通过相互作用形成的二维层状结构,进而通过ABAB...堆积方式形成三维超分子结构。最后,讨论了热力学和动力学因素对配位聚合物结构的影响。5.合成了六种羧酸官能化硅烷,包括二(4-羧基苯基)二甲基硅烷(L18)、三(4-羧基苯基)甲基硅烷(L19)、四(4-羧基苯基)硅烷(L20)、二(3-羧基苯基)二甲基硅烷(L21)、三(3-羧基苯基)甲基硅烷(L22)和四(3-羧基苯基)硅烷(L23),通过红外光谱、1H核磁共振谱、13C核磁共振谱和高分辨质谱等手段表征了其结构。讨论了两种合成路线对产物的影响,寻找出一种适合合成羧酸官能化硅烷的最优反应路线。以L22和L23为配体构筑了两种配位聚合物,[Cd3(L22)2(Py)4]·4H2O (CP-6)和[Cd4(L23)2(DMF)2(H2O)6(EtOH)]·4DMF (CP-7)。CP-6是以配体L22和Cd(NO3)2通过双相反应得到的,是一种以高度扭曲的三金属八面体的次级构建单元(SBU)为基础构建的(6,3)三维多孔结构,存在正方形和椭圆形孔洞,水分子填充在孔洞内。CP-7是以配体L23和Cd(NO3)2通过单相反应得到的,存在两种由金属原子构成的节点,一种是单个Cd(Ⅱ)金属,一种是由三金属组成的金属簇,L23作为四面体的构件,与节点连接形成一种二维(4,4)层状结构,进而通过ABCD...堆积方式得到三维多孔超分子结构。更多还原

【Abstract】 Functionalized silanes are defined as the small organosilicon compounds with functional groups and can be divided into two types:π-type and heteroatom-type. Organosilicon compounds possess many unique characteristics because silicon atom can provide 3d unoccupied orbitals. On the one hand, they can serve as ligands owing to 7r-type and heteroatom-type groups providing delocalized electron and isolated electron, and can be interacted with metal ions to form small metal complexes or coordination polymers through coordination assembly. Compared to the common metal complexes, these silicon-based metal complexes have many novel structures and better optical, electronic and magnetic properties and could be potentially applied in many fields, such as electroluminescent devices, sensor technology et al owing to the unique structure and electronic properties of silicon atom. On the other hand, compared to conventional carbon compounds, functionalized silanes have many advantages, such as more accessible synthesis, high thermal stability and high color purity. Thus they have been applied in extensive areas, including organic light emitting devices, chemical sensors or biosensors et al. In this dissertation, investigations have been carried out and focused on the synthesis, assembly and properties of nitrogen-heterocycle and carboxylate functionalized silanes. The main contents are as follows:1. A series of precursors of phenyl-bridged functionalized silanes—bromophenyl silanes have been synthesized, including products 1～7 with bromine in the p- position of silicon, products 8-11 with bromine in the m- position of silicon and pheyl-bridged product 13, then characterized by FTIR、1H NMR and 13C NMR. After the effects of different reaction methods on the products have been investigated and a suitable synthetic condition has been chosen as the synthesis of bromophenyl silanes. The condition is using organolithium reagent, anhydrous ether as the reaction solvent and-78℃as the reaction temperature.2. Bromophenyl silanes as the starting materials, a series of phenyl-bridged imidazole functionalized silanes, including Bis(4-(1H-imidazol-1-yl)phenyl)dimethyl silane (L1), Tri(4-(1H-imidazol-1-yl)phenyl)methylsilane (L2), Bis(4-(1H-imidazol-1-yl)phenyl)diphenylsilane (L3), Tri(4-(1H-imidazol-1-yl)phenyl)phenylsilane (L4), [Bis(4-(1H-imidazol-1-yl)phenyl)](4-bromophenyl)phenylsilane (L5) and [Tri(4-(1H-imidazol-1-yl)phenyl)](4-bromophenyl)silane (L6) have been synthesized according to Ullmann condensation reaction and characterized by FTIR,1H NMR,13C NMR and mass spectroscopy. The effects of several different reaction systems on productions have been studied and two proper reaction systems have been obtained. They all display high thermal stability, are fluorescent with emission in the region of violet to blue, and possess large HOMO-LUMO energy gaps ranging from 4.9585 to 5.1879 eV. Thus they could be potentially used as blue emitters or hole blocking materials in OLEDs. Moreover, the metal ion titrations based on Ag (Ⅰ) and compounds 1-4 reveal that these ligands perform distinguishable fluorescence response with increase of Ag (Ⅰ) ions.3. Bromophenyl silanes as the starting materials, a series of phenyl-bridged nitrogen-heterocycle functionalized silanes have been synthesized via Ullmann condensation reaction, including Bis(4-(1H-pyrazol-1-yl)phenyl)dimethylsilane (L8), Bis(3-(1H-pyrazol-1-yl)phenyl)dimethylsilane (L9), Tri(4-(1H-pyrazol-1-yl)methyl silane (L10), Bis(4-(1H-benimidazol-1-yl)phenyl)dimethylsilane (L11), Bis(3-(1H-benimidazol-1-yl)phenyl)dimethylsilane (L12), Bis(4-methyl-(1H-imidazol-1-yl) phenyl)dimethylsilane (L13), (3-(1H-imidazol-1-yl)phenyl)trimethylsilane (L14), Bis(3-(1H-imidazol-1-yl)phenyl)dimethylsilane (L15), Tri(4-(1H-imidazol-1-yl) phenyl)methylsilane (L16) and Bis(4-(1H-imidazol-1-yl)phenyl)vinylmethylsilane (L17) and then characterized by FTIR,1H NMR,13C NMR and mass spectroscopy. They all display high thermal stability, are fluorescent with emission in the region of violet to blue. Thus they could be potentially used as blue emitters in OLEDs. The investigations on the optical properties of different nitrogen-heterocycle functionalized silanes reveal that three approaches, including highπ-conjugated system, multi- functional groups introduced in the compound and functional groups locating in the p- position with phenyl bridging are effective ways to increase the quantum yield of them.4. Based on a semirigid imdazole functionalized silane, Bis(4-(1H-imidazol-1-yl) phenyl)dimethylsilane (L1), five novel coordination polymers, [Ag(Ll)]0.5[Ag(Ll)]2·2.5ClO4·5H2O (CP-1), Ag(Ll)PF6·H2O (CP-2), MnCl2(L1)2 (CP-3), Cu(L1)Br (CP-4) and Cu(L1)Cl (CP-5) have been constructed and the structures were determined by single crystal X-ray diffraction. The results reveal that all of them were built from one-dimensional (1D) chains, which indicate that L1 is an excellent linear ligand. CP-1 is a 3D-braided porous metal-organic framework via self-assembly of two series of 1D polymer chains through both braiding and interpenetrating. CP-1 consists of two distinct kinds of channels with different sizes and shapes along a and b directions occupied by perchlorate anions and water molecules. Complex CP-1 possesses selective anion exchange with PF6- and BF4- anions over CF3SO3-/PF6-/ BF4-. CP-3 contains a 2D layered structure constructed from 1D chains with a 34-memebered macrometallocycle as the subunit. CP-4 and CP-5 belong to 2D layered structure built from 1D zigzag chains, then 3D supramolecular structures are formed through ABAB…stacking between adjacent 2D layers. At last, dynamic and thermodynamic effects on the structures of the coordination polymers are also discussed.5. Six carboxylate functionalized silanes, have been synthesized, including Bis(4-carboxyphenyl)dimethylsilane (L18), Tri(4-carboxyphenyl) methylsilane (L19), Tetra(4-carboxyphenyl)silane (L20), Bis(3-carboxyphenyl)dimethylsilane (L21), Tri (3-carboxyphenyl)methylsilane (L22) and Tetra(3-carboxyphenyl)silane (L23) and then characterized by FTIR,1H NMR,13C NMR and mass spectroscopy. Two synthetic routes on these compounds have been discussed and a suitable route for carboxylate functionalized silanes has been achieved.Based on L22 and L23, two novel coordination polymers, [Cd3(L22)2(Py)4]·4H2O (CP-6) and [Cd4(L23)2(DMF)2(H2O)6(EtOH)]·4DMF (CP-7) have been constructed and their structures were determined by single crystal X-ray diffraction.. CP-6 was obtained from L22 and Cd(NO3)2 through double phase reaction and is a 3D porous (6,3) network containing high disordered octahedral trimetallic secondary buliding units (SBUs). CP-6 consists of square and ellipse channels occupied by water molecules. CP-7 was built from L23 and Cd(NO3)2 through single phase reaction. In CP-7, two nodes based on metal ions exist. One is single Cd(II) and the other is trimetallic SBUs. L23 acts as tetrahedral spacers and forms an 2D (4,4) layered network. A 3D supramolecular structure is formed through ABCD…stacking between 2D layers.更多还原