Synthesis,structures,and properties of metal-organic frameworks based on bipyridyl ligands and isophthalic acid  

双吡啶基配体和间苯二甲酸构筑的金属有机骨架的结构及性质

作　　者：HOU Jimin LI Mengyang GONG Chunhua ZHANG Shaozhuang ZHAN Caihong XU Hao XIE Jingli 侯纪敏;李梦洋;宫春华;张少壮;詹才宏;徐昊;谢景力(浙江师范大学化学与材料科学学院,金华321004;嘉兴大学生物与化学工程学院,嘉兴314001;嘉兴南湖学院新材料工程学院,嘉兴314001)

机构地区：[1]College of Chemistry and Materials Science,Zhejiang Normal University,Jinhua,Zhejiang 321004,China [2]College of Biological,Chemical Sciences and Engineering,Jiaxing University,Jiaxing,Zhejiang 314001,China [3]School of Advanced Materials and Engineering,Jiaxing Nanhu University,Jiaxing,Zhejiang 314001,China

出　　处：《无机化学学报》2025年第3期549-560,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21771088)资助。

摘　　要：(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.合成了2种双吡啶基配体:(2E,6E)-4-甲基-2,6-双(吡啶-3-基亚甲基)环己-1-酮(L_(1))和4-甲基-2,6-双[(E)-4-(吡啶-4-基)亚苄基]环己-1-酮(L_(2)),并在溶剂热条件下,以其与间苯二甲酸(H_(2)IP)和过渡金属反应,制备了4种金属有机骨架(MOFs)材料:[Zn(IP)(L_(1))]_n(1)、{[Cd(IP)(L_(1))]·H_(2)O}_n(2)、{[Co(IP)(L_(1))]·H_(2)O}_n(3)、[Zn(IP)(L_(2))(H_(2)O)]_n(4)。通过单晶X射线衍射、粉末X射线衍射、热重和元素分析对其进行了表征。单晶X射线衍射分析表明,MOF 1属于单斜晶系P2_(1)/n空间群,MOF 2~4都属于三斜晶系P1空间群。1~3具有二维结构,其中2和3具有相似结构,4为一维链状结构。光催化降解有机染料性能研究结果表明,1~3对罗丹明B(RhB)和盐酸副玫瑰苯胺(PH)有一定降解活性。以4作为催化剂用于苯甲醛衍生物和丙二腈的Knoevenagel缩合反应,催化结果表明,4可在3 h内催化生成产物,可循环利用3次并保持其活性。初步探究了4催化Knoevenagel缩合反应的机理。

关 键 词：bipyridyl ligands metal⁃organic frameworks photocatalytic degradation Knoevenagel condensation 

分 类 号：O614.241[理学—无机化学] O614.242[理学—化学] O614.812