| 摘要: | 本論文主旨為研究1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6- trimethylbenzene (TBzIm)搭配不同羧酸根配子及鈷、鋅、鎘二價金屬離子之水浴自組裝合成反應，共合成五種配位聚合物，並研究得到的配位聚合物之結構與性質，本論文分成三部分探討。(一)利用有機配子TBzIm和4-aminobenzoic acid (4-abc)與鎘金屬離子，進行水浴自組裝反應，得到配位聚合物1。以有機配子TBzIm和4-abc與CdCl2•2.5H2O反應，於80 °C下反應得到化合物{[Cd5Cl10(TBzIm)4]•2H2O}n (1)，化合物1為三維孔洞結構，且孔道中含有規律排列的客分子水。結構中經由特殊的五核鎘做為結構單元，再經由TBzIm橋接此結構單元形成無限擴張的三維結構。在此結構中有機配子TBzIm為文獻中少見的intermediate構型，苯咪唑上的苯環為向內收縮形式。若是不加入4-abc亦可得到此化合物，只是晶形為細針狀較不易解晶。(二)使用TBzIm搭配鋅金屬離子或鈷金屬離子，混合剛性羧酸基2,6-naphthalenedicarboxylic acid (2,6-ndc)或1,4-naphthalenedicarboxylic acid (1,4-ndc)進行水浴自組裝反應，得到配位聚合物2?3。以有機配子TBzIm和 2,6-ndc與Zn(NO3)2‧6H2O反應，於80 °C下反應得到化合物{[Zn3(TBzIm)2(2,6-ndc)3]•5DMF•5H2O}n (2)；以有機配子TBzIm和 1,4-ndc與CoCl2‧6H2O反應，於80 °C下反應得到化合物{[Co3Cl2(TBzIm)2(1,4-ndc)2]}n (3)，所得到的化合物皆為三維pillared-layer structure。其中化合物3結構中TBzIm為文獻中少見的intermediate構型，苯咪唑上的苯環為向內形式。(三)使用TBzIm搭配dimethylmalonic acid (dmm)以及鈷金屬離子，進行水浴自組裝反應，得到配位聚合物4?5。以有機配子TBzIm和dmm與Co(C2H3O2)2•4H2O反應，在80 °C下反應得到化合物{[Co3(TBzIm)3(dmm)2(HCO2)][HCO2]•8H2O}n (4)；若是將反應濃度減半，同樣以有機配子TBzIm和dmm與Co(C2H3O2)2•4H2O反應，在80 °C下反應得到化合物{[Co3(TBzIm)2(dmm)3]•2DMF•H2O}n (5)，化合物4?5皆為二維層狀結構，兩者反應中，雖然比例相同，但因濃度不同，反應速度與晶體成長速度也不同，因此得到不同結構的產物。In this thesis, metal–organic coordination frameworks were prepared by reacting a ligand, 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm), with Co2+, Zn2+, Cd2+ and different carboxylate ligands under 80 °C conditions. The synthetic method, structures and physical properties of these compounds were investigated.We report five compounds in this study, {[Cd5Cl10(TBzIm)4]•2H2O}n (1), {[Zn3(TBzIm)2(2,6-ndc)3]•5DMF•5H2O}n (2), {[Co3Cl2(TBzIm)2(1,4-ndc)2]}n (3), {[Co3(TBzIm)3(dmm)2(HCO2)][HCO2]•8H2O}n (4), {[Co3(TBzIm)2(dmm)3]•2DMF•H2O}n (5). A semi-rigid tripodal ligand, TBzIm, was first reacted with CdCl2•2.5H2O and 4-aminobenzoic acid (4-abc) to afford Compound 1 under 80 °C conditions. Compound 1 is comprised of a 3D porous metal–organic framework,which is built up from pentanuclear Cd2+ center repeating units. The pore of compound 1 is contains guest water molecules. In this case, TBzIm remains in a rare intermediate conformation.In the second part, TBzIm was reacted with different metal ions and carboxylate ligands (2,6-naphthalenedicarboxylic acid, 2,6-ndc and 1,4-naphthalenedicarboxylic acid, 1,4-ndc) to afford a two 3D pillar-layer structure at a temperature of under 80 °C. Compound 2 was produced from the self-assembly of TBzIm, Zn(NO3)2•6H2O, and 2,6-ndc. Compound 3 was prepared from TBzIm, CoCl2•6H2O, and 1,4-ndc. TBzIm remains in a rare intermediate conformation in the compound 3.In the third part, TBzIm was reacted with Co(C2H3O2)2•4H2O and dimethylmalonic acid (dmm) to produce a two layered structure at a temperature of under 80 °C. Compound 4 was prepared from TBzIm, Co(C2H3O2)2•4H2O, and dmm. The concentration of reactants is different between compounds 4 and compound 5. The concentration of compound 5 is doubled that for compound 4. The steric hindrance of TBzIm play important roles in the architectural engineering between these two crystals. |
