Synthesis and structures of cdq‑topological quaternary and(4,4,8)‑c topological quinary Zn‑MOFs with both oxalic acid and triazole ligands  

基于草酸和三氮唑的cdq拓扑四元与(4,4,8)‑c拓扑五元Zn‑MOFs的合成与结构

作　　者：LIANG Jing WANG Qian BAI Junfeng 梁婧;王倩;白俊峰(南京工业大学化学与分子工程学院,南京211816)

机构地区：[1]School of Chemistry and Molecular Engineering,Nanjing Tech University,Nanjing 211816,China

出　　处：《无机化学学报》2024年第11期2186-2192,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22271150)资助。

摘　　要：Different solvothermal reactions of ZnC2O_(4)with oxalic acid(H_(2)ox)and 1,2,4-triazole(Htrz)successfully gave a new quaternary(NJTU-Bai83,NJTU-Bai=Nanjing Tech University Bai's group)and a new quinary(NJTU-Bai84)anionic metal-organic frameworks(MOFs),where NJTU-Bai83=(Me_(2)NH_(2))2[Zn_(3)(trz)_(2)(ox)_(3)]·2H_(2)O and NJTU-Bai84=(Me_(2)NH_(2))[Zn_(3)(trz)_(3)(ox)_(2)]·H_(2)O,respectively.With the[Zn_(2)(ox)4(trz)_(2)]secondary building unit(SBU)in NJTU-Bai83 replaced by the[Zn_(3)(ox)_(2)(trz)_(6)]and planar[Zn(ox)_(2)(trz)_(2)]ones in NJTU-Bai84,2D supramolecular building layers(SBLs)are changed from the A-layer and B-layer to another A-layer,while pillars are transformed from the tetrahedral[Zn(ox)_(2)(trz)_(2)]SBU to the irregular tetrahedral[Zn(ox)_(2)(trz)_(2)]and planar[Zn(ox)_(2)(trz)_(2)]SBUs.Thus,cdq-topological quaternary NJTU-Bai83 is tuned to(4,4,8)-c new topological quinary NJTU-Bai84.Two MOFs were well characterized by powder X-ray diffraction,thermogravimetric analysis,elemental analysis,etc.CCDC:2351819,NJTU-Bai83;2351820,NJTU-Bai84.利用草酸锌与草酸(H_(2)ox)和1,2,4-三氮唑(Htrz)在不同溶剂热条件下反应,成功合成了2例新的多元阴离子型金属有机骨架(MOFs),即四元MOF(Me_(2)NH_(2))2[Zn_(3)(trz)_(2)(ox)_(3)]·2H_(2)O(NJTU-Bai83)和五元MOF(Me_(2)NH_(2))[Zn_(3)(trz)_(3)(ox)_(2)]·H_(2)O(NJTU-Bai84)。在NJTU-Bai83中,次级构筑单元(SBU)为[Zn_(2)(ox)4(trz)_(2)],而在NJTU-Bai84中,SBUs为[Zn_(3)(ox)_(2)(trz)_(6)]和[Zn(ox)_(2)(trz)_(2)]。次级构筑单元的变化导致了2D超分子层(SBL)由NJTU-Bai83中A-和B-SBL转变为NJTU-Bai84中的另一A-SBL,同时支柱由四面体[Zn(ox)_(2)(trz)_(2)]SBU转变为不规则四面体[Zn(ox)_(2)(trz)_(2)]和平面型[Zn(ox)_(2)(trz)_(2)]SBUs。有趣的是,NJTU-Bai83的cdq拓扑结构也转变为NJTU-Bai84的(4,4,8)-c新拓扑结构。2例MOFs均以粉末X射线衍射、热重和元素分析等进行了表征。

关 键 词：controlled synthesis multivariant metal-organic frameworks pillar-layer typed structures 

分 类 号：O614.241[理学—无机化学]