以多齿类羟酸为配体构筑的金属有机框架的合成、结构和性质研究
摘要
金属—有机骨架作为一种新型的分子功能材料，凭借其独特的结构可剪裁性、多样的拓扑结构和在氢气存储、离子交换、吸附、分子识别、催化以及光、电、手性拆分等领域的巨大潜在应用受到了各界科学家们越来越多的关注。依据分子工程学原理，通过选择特定几何构型的中心金属离子和特殊的有机配体，可以在一定程度上实现新型功能材料的定向设计和合成。同时，还可以通过选择功能性的中心金属离子和具有功能官能团的有机配体赋予目标化合物以多功能的性质。
本论文选择不同构型的有机配体和金属离子合成出19种金属—有机骨架。研究这些化合物的合成条件及规律，分析网络结构所属的拓扑类型，考察配体的几何构型，辅助配体对于整个结构的影响等规律，探究分子自组装原理。对化合物的热稳定性、荧光性质，吸附，离子交换进行了初步研究。
1．以5-氧-（4-苄基苯甲酸基）间苯二甲酸(H_3L1)和1,4-对苯二咪唑(BIMB)、1,4-对苯二甲基咪唑(BIIM)在水热条件下与过渡金属离子和稀土金属离子反应合成了10个新颖的化合物,它们的分子式分别为[Cu(HL1)(BIMB)]·_(0.5)H_2O (1)，[Pr(HL1)(BIMB)]·H_2O (2)，[Zn(HL1)(BIMB)_(0.5)]·H_2O (3)，[Zn_3(L1)_2(BIMB)_3]·8H_2O (4)，[Zn_3(L1)_2(BIMB)_3]·4H_2O (5)，[Zn_2(HL1)_2(BIIM)_2]·H_2O (6)，[Cu_2(HL1)_2(BIIM)_2]·H_2O (7)，[Cu(L1)(BIIM)_(0.5)(H_2O)]·H_2O (8)，[Cu_2(L1)(BIIM)(μ_3-OH)]·3H_2O (9)[Cu_(1.5)(L1)(BIIM)_(1.5)]·2H_2O (10)，化合物1，2和3都是二维4连接的层状结构，化合物4是了一个三维(3,4)连接三重互穿的网络结构，当我们将4的反应条件不变，温度升高到180度，我们得到了结构更加复杂的化合物5；化合物6和化合物7是破浪形的二维(4,4)层；化合物8和10的骨架结构都是(3,4)–混连接的三维网络；化合物9的四核Cu SBUs连接十个有机配体，构筑了三维(3,10)连接的网络结构。
2．以5-氧-（4-苄基苯甲酸基）间苯二甲酸(H_3L1)和苯并咪唑(BENIM)、1,2，4-三氮唑(1,2,4-triazole)在水热条件下与过渡金属离子反应合成了5个新颖的化合物,它们的分子式分别为[Zn (HL1)(BENIM)](11)，[Co (HL1)(BENIM)](12)[Co_2(HL1)(BENIM)_2(μ_3-OH)]·H_2O (13)，[Co_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](14)和[Ni_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](15)，化合物11和12同构，14和15同构，化合物11是含有两种不同类型的螺旋链的二维层网络；化合物13的四核CoSBUs通过L1配体的羧酸基团连接成二维(3,6)连接层状结构；化合物14是三维(3,8)连接的网络拓扑。
3．以5-氧-（3-苄基苯甲酸基）间苯二甲酸(H3L2)和1,4-对苯二咪唑(BIMB)在水热条件下与过渡金属Zn~(2+)离子反应合成了2个新颖的化合物,它们的分子式分别为[Zn_2(L2)(BIMB)(μ_2-OH)](16)[Zn_3(L2)_2(BIMB)_3]·4H_2O (17)，化合物16通过平行的层网络互穿，形成了2D→3D互锁的框架结构；化合物17产生于中性pH条件，得到了(3,4)连接自穿的三维网络。
4．以两个长链半刚性羧酸(H_3L_3)和(H_3L_4)为配体，在溶剂热条件下与过渡金属Zn~(2+)离子反应合成了2个新颖的化合物,它们的分子式分别为[Zn_2(L3)(H_2O)]·(NO_3)·DMF(18)，[Zn_2(L4)(H_2O)]·(NO_3)·0.2DMF (19)，两种化合物同构，探讨了它们在吸附、主体框架交换客体稀土离子、碘离子，以及客体离子对主体框架荧光强度的影响等方面的性质。
Metal-organic frameworks (MOFs) as a newly-identified functionalmolecule-based materials, have attracted much more attentions because of theirflexible tailoring, various topologies and promising applications in hydrogen storage,ion-exchange, adsorption, molecular recognization, catalysts along with optics,electrics and enantioselective separation. According to the principle of molecularengineering, it is possible that rational design and synthesis of novel multifunctionalmaterials by selecting certain geometric metal ions and special organic ligands. At thesame time, MOFs can be endowed with multifunctional properties by selectingfunctional metal ions and organic ligands with functional groups.
In this dissertation, we have focused our study on the influence of the metal ions,organic ligands and secondary ligands on the building blocks and structures of MOFsby the hydrothermal reaction. Twenty-one new coordination compounds have beensynthesized by using novel organic ligands and metal ions. The study on syntheticconditions and rules for these new compounds, topological analyses, and theexploration of relationships between structures and properties for these newcompounds are also carried out. These compounds have been structurallycharacterized by elemental analyses, IR, XRPD, TG and single crystal X-raydiffractions. In addition, the thermal stabilities, fluorescent activity, photovoltagetransients, adsorption and ion-exchange of these compounds have been studied.
1. Ten novel3D compounds,[Cu(HL1)(BIMB)]·_(0.5)H_2O (1),[Pr(HL1)(BIMB)]·H_2O (2),[Zn(HL1)(BIMB)_(0.5)]·H_2O (3),[Zn_3(L1)_2(BIMB)_3]·8H_2O(4),[Zn_3(L1)_2(BIMB)_3]·4H_2O (5)，[Zn_2(HL1)_2(BIIM)_2]·H_2O (6),[Cu_2(HL1)_2(BIIM)_2]·H_2O (7),[Cu(L1)(BIIM)_(0.5)(H_2O)]·H_2O (8),[Cu_2(L1)(BIIM)(μ_3-OH)]·3H_2O (9) and [Cu_(1.5)(L1)(BIIM)_(1.5)]·2H_2O (10) have beensynthesized using the traditional hydrothermal methods. Compound1,2and3showsa2D4-connected network. Complex4is obtained on a higher pH value than3, whichis3D threefold interpenetrating (3,4)-connected net. Compound6and7is a2D (4,4)sheet with (412·63) topology. Compound8and10displays a3D (3,4)-connectedthreefold interpenetration network, which is constructed by H_3L1and BIIM ligands.Compound9is a3D (3,10)-connected network.
2. Five compounds with different dimensionalities,[Zn (HL1)(BENIM)](11), [Co (HL1)(BENIM)](12),[Co_2(HL1)(BENIM)_2(μ_3-OH)]·H_2O(13),[Co_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](14) and [Ni_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](15)have been prepared under hydrothermal conditions. Compound11and12areisostructural; Compound14and15are isostructural. Compound11displays a new2Dframework constructed by two types of helical chains; Compound13is a2D(3,6)-connected net. Compound14is a3D (3,8)-connected network
3. Two compounds with different dimensionalities,[Zn_2(L2)(BIMB)(μ_2-OH)](16)and [Zn_3(L2)_2(BIMB)_3]·4H_2O(17) have been prepared under hydrothermal conditions.Compound16is a2D→3D interlocking framework. Compound17adopts a3D(3,4)-connected self-penetrating network.
4.[Zn_2(L3)(H_2O)]·(NO_3)·DMF(18) and [Zn_2(L4)(H_2O)]·(NO_3)·0.2DMF(19), twoisostructural2D-2D parallel-3D inclined interpenetrating polycatenane-likemetal–organic frameworks were successfully constructed based on length-adjustedtricarboxylate ligands. With the merit of being microporous, Compound18canserve as host for encapsulating lanthanide cations and I2to exhibit luminescentsensing and rapid adsorption of iodine.
本论文选择不同构型的有机配体和金属离子合成出19种金属—有机骨架。研究这些化合物的合成条件及规律，分析网络结构所属的拓扑类型，考察配体的几何构型，辅助配体对于整个结构的影响等规律，探究分子自组装原理。对化合物的热稳定性、荧光性质，吸附，离子交换进行了初步研究。
1．以5-氧-（4-苄基苯甲酸基）间苯二甲酸(H_3L1)和1,4-对苯二咪唑(BIMB)、1,4-对苯二甲基咪唑(BIIM)在水热条件下与过渡金属离子和稀土金属离子反应合成了10个新颖的化合物,它们的分子式分别为[Cu(HL1)(BIMB)]·_(0.5)H_2O (1)，[Pr(HL1)(BIMB)]·H_2O (2)，[Zn(HL1)(BIMB)_(0.5)]·H_2O (3)，[Zn_3(L1)_2(BIMB)_3]·8H_2O (4)，[Zn_3(L1)_2(BIMB)_3]·4H_2O (5)，[Zn_2(HL1)_2(BIIM)_2]·H_2O (6)，[Cu_2(HL1)_2(BIIM)_2]·H_2O (7)，[Cu(L1)(BIIM)_(0.5)(H_2O)]·H_2O (8)，[Cu_2(L1)(BIIM)(μ_3-OH)]·3H_2O (9)[Cu_(1.5)(L1)(BIIM)_(1.5)]·2H_2O (10)，化合物1，2和3都是二维4连接的层状结构，化合物4是了一个三维(3,4)连接三重互穿的网络结构，当我们将4的反应条件不变，温度升高到180度，我们得到了结构更加复杂的化合物5；化合物6和化合物7是破浪形的二维(4,4)层；化合物8和10的骨架结构都是(3,4)–混连接的三维网络；化合物9的四核Cu SBUs连接十个有机配体，构筑了三维(3,10)连接的网络结构。
2．以5-氧-（4-苄基苯甲酸基）间苯二甲酸(H_3L1)和苯并咪唑(BENIM)、1,2，4-三氮唑(1,2,4-triazole)在水热条件下与过渡金属离子反应合成了5个新颖的化合物,它们的分子式分别为[Zn (HL1)(BENIM)](11)，[Co (HL1)(BENIM)](12)[Co_2(HL1)(BENIM)_2(μ_3-OH)]·H_2O (13)，[Co_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](14)和[Ni_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](15)，化合物11和12同构，14和15同构，化合物11是含有两种不同类型的螺旋链的二维层网络；化合物13的四核CoSBUs通过L1配体的羧酸基团连接成二维(3,6)连接层状结构；化合物14是三维(3,8)连接的网络拓扑。
3．以5-氧-（3-苄基苯甲酸基）间苯二甲酸(H3L2)和1,4-对苯二咪唑(BIMB)在水热条件下与过渡金属Zn~(2+)离子反应合成了2个新颖的化合物,它们的分子式分别为[Zn_2(L2)(BIMB)(μ_2-OH)](16)[Zn_3(L2)_2(BIMB)_3]·4H_2O (17)，化合物16通过平行的层网络互穿，形成了2D→3D互锁的框架结构；化合物17产生于中性pH条件，得到了(3,4)连接自穿的三维网络。
4．以两个长链半刚性羧酸(H_3L_3)和(H_3L_4)为配体，在溶剂热条件下与过渡金属Zn~(2+)离子反应合成了2个新颖的化合物,它们的分子式分别为[Zn_2(L3)(H_2O)]·(NO_3)·DMF(18)，[Zn_2(L4)(H_2O)]·(NO_3)·0.2DMF (19)，两种化合物同构，探讨了它们在吸附、主体框架交换客体稀土离子、碘离子，以及客体离子对主体框架荧光强度的影响等方面的性质。
Metal-organic frameworks (MOFs) as a newly-identified functionalmolecule-based materials, have attracted much more attentions because of theirflexible tailoring, various topologies and promising applications in hydrogen storage,ion-exchange, adsorption, molecular recognization, catalysts along with optics,electrics and enantioselective separation. According to the principle of molecularengineering, it is possible that rational design and synthesis of novel multifunctionalmaterials by selecting certain geometric metal ions and special organic ligands. At thesame time, MOFs can be endowed with multifunctional properties by selectingfunctional metal ions and organic ligands with functional groups.
In this dissertation, we have focused our study on the influence of the metal ions,organic ligands and secondary ligands on the building blocks and structures of MOFsby the hydrothermal reaction. Twenty-one new coordination compounds have beensynthesized by using novel organic ligands and metal ions. The study on syntheticconditions and rules for these new compounds, topological analyses, and theexploration of relationships between structures and properties for these newcompounds are also carried out. These compounds have been structurallycharacterized by elemental analyses, IR, XRPD, TG and single crystal X-raydiffractions. In addition, the thermal stabilities, fluorescent activity, photovoltagetransients, adsorption and ion-exchange of these compounds have been studied.
1. Ten novel3D compounds,[Cu(HL1)(BIMB)]·_(0.5)H_2O (1),[Pr(HL1)(BIMB)]·H_2O (2),[Zn(HL1)(BIMB)_(0.5)]·H_2O (3),[Zn_3(L1)_2(BIMB)_3]·8H_2O(4),[Zn_3(L1)_2(BIMB)_3]·4H_2O (5)，[Zn_2(HL1)_2(BIIM)_2]·H_2O (6),[Cu_2(HL1)_2(BIIM)_2]·H_2O (7),[Cu(L1)(BIIM)_(0.5)(H_2O)]·H_2O (8),[Cu_2(L1)(BIIM)(μ_3-OH)]·3H_2O (9) and [Cu_(1.5)(L1)(BIIM)_(1.5)]·2H_2O (10) have beensynthesized using the traditional hydrothermal methods. Compound1,2and3showsa2D4-connected network. Complex4is obtained on a higher pH value than3, whichis3D threefold interpenetrating (3,4)-connected net. Compound6and7is a2D (4,4)sheet with (412·63) topology. Compound8and10displays a3D (3,4)-connectedthreefold interpenetration network, which is constructed by H_3L1and BIIM ligands.Compound9is a3D (3,10)-connected network.
2. Five compounds with different dimensionalities,[Zn (HL1)(BENIM)](11), [Co (HL1)(BENIM)](12),[Co_2(HL1)(BENIM)_2(μ_3-OH)]·H_2O(13),[Co_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](14) and [Ni_(1.5)(L1)(1,2,4-triazole)(μ_2-OH)](15)have been prepared under hydrothermal conditions. Compound11and12areisostructural; Compound14and15are isostructural. Compound11displays a new2Dframework constructed by two types of helical chains; Compound13is a2D(3,6)-connected net. Compound14is a3D (3,8)-connected network
3. Two compounds with different dimensionalities,[Zn_2(L2)(BIMB)(μ_2-OH)](16)and [Zn_3(L2)_2(BIMB)_3]·4H_2O(17) have been prepared under hydrothermal conditions.Compound16is a2D→3D interlocking framework. Compound17adopts a3D(3,4)-connected self-penetrating network.
4.[Zn_2(L3)(H_2O)]·(NO_3)·DMF(18) and [Zn_2(L4)(H_2O)]·(NO_3)·0.2DMF(19), twoisostructural2D-2D parallel-3D inclined interpenetrating polycatenane-likemetal–organic frameworks were successfully constructed based on length-adjustedtricarboxylate ligands. With the merit of being microporous, Compound18canserve as host for encapsulating lanthanide cations and I2to exhibit luminescentsensing and rapid adsorption of iodine.
引文
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