晶體工程：多孔性、功能性配位聚合物的自組裝和結構分析

Abstract

中文摘要 本論文應用晶體工程的策略，採用室溫自組裝法合成十個配位聚合物和一個四核矩形分子化合物。{[Cu3Cl2(4-ptz)4(H2O)2]3DMF5H2O}n （1, 4-H-ptz = 5-(4-pyridyl)tetrazole）是電中性的三維網狀結構，以連接數為八的三銅金屬簇作連結中心，配合直線型的配子4-ptz，是稀有的多孔性體心立方型態結構。{[M2(CA)3][(H3O)2(phz)3]2CH3COCH32H2O }n （M = Cu, 2; M = Cd, 4; M = Zn, 5; M = Co, 6; CA = chloranilate; phz = phenazine）由陰離子性金屬–有機配位層和陽離子性氫鍵–有機層，藉著完美的π–π作用交互堆疊形成三維結構，具有孔徑達8 的一維孔道。在真空下移除化合物2的客分子後，可以得到結構仍然維持完好的化合物{[Cu2(CA)3][(H3O)2(phz)3]}n (3)，可以由單晶結構來證明。{[Cd3(CA)3(dptz)2(H2O)2]2THF7H2O}n（7, dptz = 3,6-di-2-pyridyl- 1,2,4,5-tetrazine）是電中性的二維網狀結構，含有連接數為三和四的兩種節點，並具有兩種大小不同的孔洞。{[Cu2(CA)2(2,2’-bpym)]2DMF}n （8, 2,2’-bpym = 2,2’-bipyrimidine）由電中性的二維網狀結構所堆疊而成，具有達5 的一維孔道。{[Cd6(CA)9](H-1,3-bpp)4(H3O)2(H2O)8 (CH3CN)4}n（9, 1,3-bpp = 1,3-bis(4-pyridyl)propane）由陰離子性的二維網狀結構所堆疊而成，H-1,3-bpp配子以陽離子的模式存在於孔洞之中，調控了結構的堆疊模式。{[Cd(CA)2]2NH2(CH3)2}n (10) 是三維陰離子性的鑽石型結構，具有三維互穿的孔道系統。在同時的情況下，孔道中的陽離子NH2(CH3)2+ 是由溶劑分子DMF水解反應產生的。[Cd4Cl4(pcaph)4] •4H2O （11, H-pcaph = pyridine-2-carboxylic acid pyridine-2-ylmethylene-hydrazide）是dptz配子在自組裝過程中轉換型態產生新型配子pcaph，並同步形成的四核矩形分子。對於這些化合物的結構，會以X-光單晶繞射法作深入的分析。

Abstract Based on efficient synthetic strategies, ten metal–organic frameworks and one tetranuclear molecular rectangle have been synthesized at ambient temperature by a single-step self-assembly process. The porous bcu-type framework of {[Cu3Cl2(4-ptz)4(H2O)2]3DMF5H2O}n (1) was assembled from 5-(4-pyridyl)tetrazole (4-H-ptz) as a bridging ligand and an eight-connecting tricopper cluster as a building block. This is the first bcu-type structure with an eight-connecting polynuclear metal cluster unit. The crystal structures of {[M2(CA)3][(H3O)2(phz)3]2CH3COCH32H2O }n （M = Cu, 2; M = Cd, 4; M = Zn, 5; M = Co, 6; CA = chloranilate; phz = phenazine）show that the assembly of the isostructural 3D networks is based on a combination of two types of grid-building subunits : an anionic metal–organic coordination honeycomb grid, and a cationic hydronium–ion–mediated organic honeycomb grid. The inorganic and organic honeycomb nets are perfectly π–π stacked, creating a 1D channel with a pore diameter of about 8 . The solid framework retains its rigidity upon removal of the guest molecules under high vacuum to form compound {[Cu2(CA)3][(H3O)2(phz)3]}n (3). The neutral 2D network of {[Cd3(CA)3(dptz)2(H2O)2]2THF7H2O}n (7, dptz = 3,6-di-2-pyridyl-1,2,4,5-tetrazine) consists of three- and four-connected nodes and forms two types of pores. The crystal structure of {[Cu2(CA)2(2,2’-bpym)] 2DMF}n (8, 2,2’-bpym = 2,2’-bipyrimidine) is based on a neutral metal–organic coordination honeycomb network and contains a 1D channel with a pore diameter of about 5 . The crystal structure of {[Cd6(CA)9](H-1,3-bpp)4(H3O)2(H2O)8(CH3CN)4}n (9, 1,3-bpp = 1,3-bis (4-pyridyl)-propane) is composed of an anionic 2D honeycomb layer and tuned by a H-1,3-bpp cation in the pores. The diamiondoid structure of {[Cd(CA)2]2NH2(CH3)2}n (10) contains a 3D intersecting channel system. The guest cation NH2(CH3)2+ was obtained from an in situ hydrolysis reaction of the solvent dimethylformamide. The tetracadmium molecular rectangle of [Cd4Cl4(pcaph)4] •4H2O (11, H-pcaph = pyridine-2-carboxylic acid pyridin-2-ylmethylene-hydrazide) is formed from a single-step self-assembly process. The new type ligand, pcaph, was produced via an in situ ligand transformation reaction at ambient temperature. Their structures have been characterized by single-crystal X-ray analyses.