Synthesis Of Asymmetric Conjugate Quadruple Nitrogen Heterocyclic Organic Molecules With D-A-D-A Type

The nitrogen-containing heterocyclic compounds occupy very important position in areas such as pesticide, medicine and bioscience, and asymmetric conjugate quadruple nitrogen heterocyclic organic molecules which contains azole with the D-A-D-A type has unique optical properties, and it can be used as optical material. Therefore, synthesis of these compounds has been hot spots in the field of organic synthesis.We have designed and synthesized a series of asymmetric conjugate quadruple nitrogen heterocyclic organic molecules with D-A-D-A type mainly through Sonogashira coupling reaction and Huisgen1,3-dipolar cycloaddition (CuAAC). The structures of these compounds were pyrrole-pyridazine-azole-pyridine. Meanwhile, we also synthesized a serious of compounds with the structure of pyrrole-pyridazine-azole using the same method. The target compounds are new and have not been reported. These compounds have been charactered by1H-NMR,13C-NMR and HRMS and melt point.Meanwhile, We assembled seven new coordination polymers using a ragid4,4’-su lfonyldibenzoic acid ligand (H2sdba)with different metal ions, namely,{[Co3(sdba)3·2H2O·DMF]·2DMF}n (1),{[Co2(sdba)·(μ3-OH)·(trz)·H2O]·H2O}n (2),{[Co2(sdba)·(μ3-OH)·(atz)·H2O]·H2O}n (3),{[Co(sdba)·(ti)2·H2O]·1.5H2O}n (4),{[Cu(sdba)·H2O]·1.5H2O}n (5),{[Cu2(sdba)·(μ3–OH)·(trz)·H2O]·H2O}n (6),{[Zn2(sdba)·(atz)2·]·0.5H2O}n (7)，(H2sdba=4,4’-sulfonyldibenzoic acid, Htrz=1H-1,2,4-triazole, Hatz=1H-1,2,4-triazol-3-amine, Hti=4-(1H-benzo[d]imidazol-2-yl)thiazole). X-ray single-crystal diffraction shows that2-3,6and7displays novel three-dimensional (3D) framework with the help of ragid organic molecules (Htrz, Hatz, and Hti). With the help of ragid organic molecules (Htrz, Hatz, and Hti)，the solvent resistance of compounds2-4,6and7are better than compounds1and5, which provides a method for praparing useful solvent resistant MOFs.