【摘要】：金屬-有機(jī)配合物在光學(xué)、磁性、催化、氣體吸附和分離等方面具有優(yōu)良的性能,受到人們廣泛關(guān)注,已成為當(dāng)今配位化學(xué)的研究熱點(diǎn)。有機(jī)配體的精心選擇和設(shè)計(jì)在晶體工程及超分子的構(gòu)建中十分重要。有機(jī)羧酸和含氮類(lèi)配體的配位方式多樣,配位能力強(qiáng),一直是化學(xué)家的研究熱點(diǎn)。利用芳香羧酸a-萘乙酸(α-HNAA)或p-萘乙酸(p-HNAA)分別與2-乙基咪唑(2-Etlm)和2-丙基咪唑(2-Prlm)、苯并咪唑(bim)、5,6-二甲基苯并咪唑(DMB)、1,4-二(苯并咪唑-1-基)丁烷(bbbm)、1,4-二(5,6-二甲基苯并咪唑-1-基)丁烷(bbdmbm)、1,4-二(苯并咪唑-1-甲基)苯(bbix)、1,4-二(2-甲基苯并咪唑-1-基)丁烷(bbmb)與過(guò)渡金屬離子反應(yīng)合成了25個(gè)結(jié)構(gòu)新的配位化合物：[Mn(a-NA A)2(H2O)2] (1)、[Cu(α-NAA)2] (2)、[Zn(α-NAA)2(H2O)2] (3)、[Cu4(α-NAA)8(CH3CN) 2] (4)、[Cu(2-Etlm)2(α-NAA)2] (5)、[Ni(2-Etlm)2(α-NAA)2] (6)、[Cd(2-Etlm)2(α-NAA) 2] (7)、[Ni(2-Prlm)2(α-NAA)2] (8)、[Co(2-Prlm)2(α-NAA)2] (9)、[Cd(2-Prlm)2(α-NAA) 2] (10)、[Cu(bim)2(α-NAA)2-H2O] (11)、[Cu2(bim)4(α-NAA)4-2H2O] (12)、[Mn(bim)2(α-NAA)2-H2O] (13)、[Ni(bim)2(α-NAA)2-H2O] (14)、[Co(bim)2(α-NAA)2-H2O] (15)、[C u(DMB)2(α-NAA)2]2 (16)、[Co(DMB)2(α-NAA)2] (17)、[Ni(DMB)2(α-NAA)] (18)、[Z n(DMB)2(α-NAA)Cl] (19)、[Cd(DMB)2(α-NAA)2] (20)、[Co(bbbm)(α-NAA)2] (21)、[C o(bbdmbm)(α-NAA)2] (22)、[Ni(bbmb)(α-NAA)2] (23)、[Ni(bbix)(β-NAA)2]及[Ni (bbix)(β-NAA)2] (25)。通過(guò)元素分析、紅外光譜、粉末衍射等對(duì)配合物進(jìn)行了初步結(jié)構(gòu)表征,進(jìn)一步采用單晶X-射線衍射測(cè)試了晶體結(jié)構(gòu)。采用熱重-差熱分析、熒光光譜、循環(huán)伏安法、變溫磁化率等測(cè)試研究了配合物的熱穩(wěn)定性、熒光、電化學(xué)、磁性質(zhì)。配合物2是一維鏈狀結(jié)構(gòu),它的銅離子被五個(gè)來(lái)自五個(gè)萘乙酸根的氧原子配位形成了一個(gè)略微扭曲的四方錐幾何構(gòu)型。磁性質(zhì)研究表明：相鄰的銅離子間存在強(qiáng)的反鐵磁耦合作用。配合物11的固體樣品在加熱到50℃后,由黃色變?yōu)椴菥G色,再降至室溫后,又恢復(fù)為黃色,表明11具有熱致變色的性質(zhì)。分析了熱致變色的產(chǎn)生原因。配聚物16和17對(duì)有機(jī)染料剛果紅具有很好的催化降解活性,降解符合準(zhǔn)一級(jí)反應(yīng)動(dòng)力學(xué)。配合物16在80分鐘后的降解率達(dá)到了96.9%,可作為潛在的催化材料。配合物9、10、13、15、21、23和25表現(xiàn)出良好的熒光性能,在熒光方面具有潛在的應(yīng)用前景。這些配合物均呈現(xiàn)出較好的熱穩(wěn)定性。
[Abstract]:Metal-organic complexes have excellent properties in optics, magnetism, catalysis, gas adsorption and separation, and have been paid more and more attention, and have become the research focus of coordination chemistry. The careful selection and design of organic ligands are very important in crystal engineering and supramolecular construction. Organic carboxylic acids and nitrogen-containing ligands have a variety of coordination modes and strong coordination ability, which has been a hot research topic for chemists. Aromatic carboxylic acid a-Naphthylacetic acid (偽-HNAA) or p-Naphthylacetic acid (p-HNAA) were used with 2-ethylimidazole (2-Etlm) and 2-propylimidazole (2-Prlm), benzimidazole (bim), 5, 6-dimethyl benzimidazole (DMB), respectively. 1, 4-bis (benzimidazole-1-yl) butane (bbbm), 1, 4-bis (5, 6-dimethyl benzimidazole-1-yl) butane (bbdmbm), 1, 4-bis (benzimidazole-1-methyl) benzene (bbix), 1, 25 new coordination compounds were synthesized by the reaction of 4-bis (2-methylbenzimidazole-1-yl) butane (bbmb) with transition metal ions: [Mn (a-NA A) 2 (H2O) 2] (1), [Cu (偽-NAA) 2] (2), [Zn (偽-NAA) 2 (H2O) 2] (3), [Cu4 (偽-NAA) 8 (CH3CN) 2] (4), [Cu (2-Etlm) 2 (偽-NAA) 2] (5), [Ni (2-Etlm) 2 (偽-NAA) 2] (6), [Cd (2-Etlm) 2 (偽-NAA) 2] (7), [Ni (2-Prlm) 2 (偽-NAA) 2] (8), [Co (2-Prlm) 2 (偽-NAA) 2] (9), [Cd (2-Prlm) 2 (偽-NAA) 2] (10), [Cu (bim) 2 (偽-NAA) 2-H2O] (11), [Cu2 (bim) 4 (偽-NAA) 4-2H2O] (12), [Mn (bim) 2 (偽-NAA) 2-H2O] (13), [Ni (bim) 2 (偽-NAA) 2-H2O] (14), [Co (bim) 2 (偽-NAA) 2-H2O] (15), [C u (DMB) 2 (偽-NAA) 2] 2 (16), [Co (DMB) 2 (偽-NAA) 2] (17), [Ni (DMB) 2 (偽-NAA)] (18), [Z n (DMB) 2 (偽-NAA) Cl] (19), [Cd (DMB) 2 (偽-NAA) 2] (20), [Co (bbbm) (偽-NAA) 2] (21), [Co (bbdmbm) (偽-NAA) 2] (22), [Ni (bbmb) (偽-NAA) 2] (23), [Ni (bbix) (尾-NAA) 2] and [Ni (bbix) (尾-NAA) 2] (25). The structure of the complex was characterized by elemental analysis, infrared spectroscopy and powder diffraction, and the crystal structure was further measured by single crystal X-ray diffraction. The thermal stability, fluorescence, electrochemical and magnetic properties of the complexes were studied by thermogravimetric-differential thermal analysis, fluorescence spectroscopy, cyclic Voltammetric method and variable temperature magnetic susceptibility. Complex 2 is a one-dimensional chain structure, and its copper ions are coordinated by five oxygen atoms from five naphthoacetic acid to form a slightly twisted tetrahedral cone geometry. The study of magnetic properties shows that there is strong antiferromagnetic coupling between adjacent copper ions. The solid sample of complex 11 changed from yellow to grass green after heating to 50 鈩，

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