华侨大学 硕士学位论文 利用N、O杂配体构筑系列新颖超分子固态网络结构 姓名：杨国栋 申请学位级别：硕士 专业：应用化学 指导教师：戴劲草 20071201 硕士学位论文： 利用 N、O 杂配体构筑系列新颖超分子固态网络结构 IV 摘 要 超分子固态化合物在分子识别、传感器、磁性材料、选择性催化、离子交换、超高纯 度分离、微电子器件和非线性光电材料等多种新型功能材料领域具有潜在的广泛应用价值， 因而引起人们相当的关注。 构筑具有新颖结构和特定性能的超分子固态化合物已成为合成化 学领域最富有挑战性的课题之一。本论文围绕当前构筑超分子网络的研究热点，采用水热合 成方法，选择一些含 N、O 杂原子的配体与过渡金属离子反应，利用结构单元的自组装来构 筑具有新颖结构的超分子固态化合物，主要完成了以下几方面的工作：合成了 12 种超分 子固态化合物Ph3PCH2Ph2Zn3(tp)3Cl2n(1)； Ph3PCH2PhZn(tp)Cln(2)； Zn(tp)(tdpy)n (3) ； Ph4P2Cd2(tp)2(Htp)2(H2O)(H2O)3n(4) ； Zn(Htma)(ddm)n(5) ； Ph4PZn(tp) (H2O)2(tp)0.5n(6)；Ph3PCH2Ph2Zn(in)2(H2O)4(tp)(H2O)4n(7)；Ph4P+H3pm- a-n(8)； Ph4P+(H2tma)(H3tma)3-n(9)；Ph4P+(H2tma)(H3 tma )2- H2On(10)； dabco H3tma2 2H2On (11)； Cd(bpy)(tp)(H2O)n(12) (式中 tp = 1,4- 苯二甲酸根； tma = 1,3,5- 苯三甲酸根；pma = 1,2,4,5- 苯四甲酸根；bpy = 2,2- 联吡啶；tdpy = 4,4- 三亚甲基联吡啶；in = 异烟酸根；dabco = 三乙撑二胺；ddm = 对对 二氨基 二苯 甲烷)。对所合成的化合物 进行单晶结构测试和分析。 运用 IR、 TGA 和荧光光谱等手段对所合成的部分化合物(17， 12)进行谱学表征和性能研究。结果表明：化合物 15 是通过配位键组装的超分子固态化合 物。化合物 1 和 2 是有趣的二维类粘土层状结构，层间填充了大体积阳离子Ph3PCH2Ph+， 其中化合物 1 具有(3,6)拓扑网络结构，而化合物2 则具有(4,4)拓扑网络结构；化合物 3 是一 种波浪起伏的双重穿插的(4,4)网络结构；化合物 4 是一种加长的二维(4,4)网络结构；而化合 物 5 存在有趣的螺旋结构。化合物 611 是通过 H 键组装的超分子固态化合物。其中，化合 物 6 是由 H 键构成的二维砖墙网络；化合物 7 则为三维层柱 H 键网络结构；化合物 8 是具 有一维通道的 H 键无限链结构的芳香酸类盐；化合物 9 具有二维蜂巢状 H 键网孔结构堆积 扩展组成的三维网络；化合物 10 为单双层片错层堆积的三维 H 键蜂巢网络；化合物 11 则 是由 dabco与 tma 通过 H 组成的二维双层网络；化合物 12 是通过 p- p 作用组装的具有三维 人字型网络结构的超分子固态化合物。 这些化合物均具有较高的热稳定性和良好的光致发光 性质，在紫外- 可见光范围内出现较强的荧光发射，因而可望成为潜在的光活性材料。另外， 化合物 1 具有良好的离子交换性质，表明该化合物有可能成为潜在的催化材料和良好的 离子储存材料。 硕士学位论文： 利用 N、O 杂配体构筑系列新颖超分子固态网络结构 V 关键词：超分子固态化合物，水热合成，配位键，氢键，离子交换，谱学表征 硕士学位论文： 利用 N、O 杂配体构筑系列新颖超分子固态网络结构 VI Abstract Supramolecular solid compounds are attracting increasing attention owing to the potential discovery of novel functional materials which are expected to find applications in the areas of molecular recognition, chemical sensors, magnetic materials, selective catalysis, ion- exchange, enantiomer separation, microelectronics and nonlinear optics etc. The construction of supramolecular solid compounds with novel a rchitectures and desired functionalities represents one of the most challenging issue facing synthetic chemistry areas today. Base on the current research of building supramolecular network, we choose some containing N- or O- donor ligands reaction to the transition metal ions by hydrothermal synthesis methods, to construct supramolecular solid compounds with novel architectures. In this thesis, 12 new supramolecular solid compounds, namely, Ph3PCH2Ph2Zn3(tp)3Cl2n(1), Ph3P- CH2PhZn(tp)Cln(2), Zn(tp)(tdpy)n(3), Ph4P2Cd2(tp)2(Htp)2(H2O)(H2O)3n (4), Zn(Htma)(ddm)n (5), Ph4PZn(tp)(H2O)2(tp)0.5n (6), Ph3PCH2Ph2Zn (in)2(H2O)4(tp)(H2O)4n(7), Ph4P+H3pma-n (8), Ph4P+(H2tma)(H3tma)3-n (9), Ph4P+(H2tma)(H3tma)2- H2On (10), dabco H3tma2 2H2On (11) , and Cd(bpy)(tp)(H2O)n (12) (where tp = terephthalate, tma = trimesate，pma = pyromellitic acid, bpy = 2,2- bipyridine，tdpy = 4,4- trimethylene- dipyridine， in = Isonicotinic acid ， dabco = 1,4- diazabicyclo2,2,2octane ， ddm = PP- Diamino- Diphenyl- Methane), have been synthesized. The structures of these 12 compounds have been determined by the X - ray single crystal diffractometer. IR spectra, TGA traces and fluorescent emissions of Compounds 17 and 12 have also been characterized and analyzed. The results show that compounds 15 belong to coordination polymeric solids, of which both compounds 1 and 2 are, respectively, 2D 6- linked (3,6) and 4- linked (4,4) anionic networks with the same occupied interlayer guest Ph3PCH2Ph+ counter cations, and also crystallized to interested smectite- like lamellar architectures, while compound 3 is twofold interpenetration topology of an undulating 2D (4,4) net, compound 4 is a lengthening 2D (4,4) network, compound 5 belongs an interesting helix structure. However, compounds 611 are crystallize another supramolecular solids assembled by hydrogen bonding. These structures respectively are, compound 6, a 2D brick wall framework, compound 7, 3D pillared layer framework, compound 8, 1D infinite chain channel, compound 9, a 硕士学位论文： 利用 N、O 杂配体构筑系列新颖超分子固态网络结构 VII 3D H- bond framework assembled by 2 D honeycomb- like sheet, compound 10, a staggered 3D framework of honeycomb- like sheets, compound 11, an interested 2D bilayer network constructed by tma and dabco molecules. Compounds 12 is a 3D herringbone topology structure assembled through p- p stacking interaction. TGA traces suggest the frameworks of compounds 17 and 12 possess high thermal stability. Under an adequate excition, the intense fluorescent emissions in the range of UV- VIS can be observed in above compounds 17 and 12 in solid state at ambient temperature, indicating of good photoluminescence. This suggests that these compounds might be the excellent candidates for potential photoactive materials. In addition, compound 1