竞争配位合成的2-硝基苯甲酸根保护的一维Co(Ⅱ)/Zn(Ⅱ)配合物  

Competitive coordination in 2‑nitro benzoate protected one‑dimensional Co(Ⅱ)/Zn(Ⅱ)complexes

作　　者：崔晓琴 王佃慧 李鑫[1] 王雨欣 李婷[1] 董婧[1] 李欢[1] CUI Xiao-Qin;WANG Dian-Hui;LI Xin;WANG Yu-Xin;LI Ting;DOND Jing;LI Huan(Institute of Crystalline Materials,Shanxi University,Taiyuan 030006,China)

机构地区：[1]山西大学晶态材料研究所,太原030006

出　　处：《无机化学学报》2023年第8期1579-1586,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21972080,21503123,21871167);三晋学者和山西省“1331工程”重点创新团队资助。

摘　　要：分别以乙酰丙酮钴Co(acac)3和乙酰丙酮锌Zn(acac)2为前驱体,2-硝基苯甲酸(2-nbaH)为配体,在甲苯中进行溶剂热反应,得到了3种一维配合物[Co(H2O)(2-nba)_(2)]_(n)(Co-1)、[Co_(3)(2-nba)_(4)(acac)_(2)]n(Co-2)和[Zn_(2)(2-nba)_(4)]n(Zn-3)。对配合物进行了元素分析、红外光谱、单晶X射线衍射和紫外可见漫反射表征。在配合物Co-1中,每个Co^(2+)离子与2个桥联水分子和4个2-nba-离子配位,形成八面体构型。当2-nba-不足时,前驱体中的配体acac-会与Co^(2+)成键,得到局部结构不同的一维配合物Co-2。最突出的是,Co-2中三分之二的Co^(2+)离子呈现三角双锥构型,而另外三分之一的Co^(2+)离子与Co-1相似。Co配合物的合成方法也成功地应用于Zn(acac)2,得到了一维zigzag形的配合物Zn-3。配合物Zn-3中,Zn^(2+)离子表现为仅由2-nba-保护的{ZnO4}四面体构型。研究表明,2-nba-与acac-的竞争配位可以显著影响Co^(2+)离子的配位环境。Using tris(acetylacetonato)cobalt (Ⅲ)􀃮(Co(acac)3)and zinc (Ⅱ)􀃭acetylacetonate(Zn(acac)2)as precursors and 2-nitrobenzoic acid(2-nbaH)as ligand,three 1D complexes[Co(H_(2)O)(2-nba)_(2)]n(Co‑1),[Co_(3)(2-nba)4(acac)_(2)]_(n)(Co‑2),and[Zn_(2)(2-nba)_(4)]_(n)(Zn‑3)were obtained by solvothermal reaction in toluene.The complexes were characterized by elemental analysis,IR spectroscopy,single-crystal X-ray diffraction,and UV-Vis diffuse reflectance spectroscopy.In complex Co‑1,each Co2+ion is coordinated by two bridged water molecules and four 2-nba-ions to form an octa-hedron geometry.When 2-nba-was not sufficient,the acac-ligands from the precursor were involved in the bonding with Co^(2+),leading to another 1D complex Co‑2 with a different local structure.Most prominent is that two-thirds of the Co^(2+)ions in Co‑2 are pentagonal triangular-dipyramid,while the other one-third is similar to that of Co‑1.The synthetic method for Co was also successfully applied to Zn(acac)2 to give a 1D zigzag-shaped Zn‑3.In complex Zn‑3,the Zn^(2+)ions exhibited the{ZnO_(4)}tetrahedral geometry protected only by 2-nba-ions.The results show that the competitive coordination between 2-nba-and acac-can significantly affect the coordination environment of Co^(2+)ions.CCDC:2174510,Co‑1;2174511,Co‑2;2174512,Zn‑3.

关 键 词：一维配合物 竞争配位 2-硝基苯甲酸 钴 锌 

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