【摘要】：本文選擇2-喹啉羧酸為母體,通過對氮雜環(huán)上的羧酸基團的定性改造,設(shè)計合成出了一系列具有不對稱結(jié)構(gòu)的單邊喹啉酰胺類有機化合物,并將這類氮雜環(huán)衍生物與不同的金屬鹽反應(yīng),合成出了14種不同的配合物并得到了其單晶。通過對它們的單晶結(jié)構(gòu)、紅外光譜、紫外光譜、熒光光譜以及熱譜的分析,以及進行了量子化學的計算,來探索它們的晶體結(jié)構(gòu)和光學性質(zhì)。14個晶體分別為:[Pb(pqnthz)(OAc)](1)[Pb(pqnthz)(NO_3)(H_2O)](2)[Cd(pqnthz)I(H_2O)]·H_2O(3)[Zn(pqnthz)_2]·DMF(4)[Ni(pqnthz)_2]·DMF(5)[Co(pqnthz)_2](6)[Mn(pqnthz)_2]·DMF(7)[Zn(bqnthz)Cl(CH_3OH)](8)[Zn(bqnthz)_2]·DMF(9)[Mn(bqnthz)_2](10)[Zn(bzqnthz)_2]·H_2O(11)[Mn(bzqnthz)_2]·H_2O(12)[Co(bzqnthz)_2](13)[Ni(bzqnthz)_2](14)(式中pqnthz為去質(zhì)子化的N-丙酰-2-喹啉甲酰肼;bqnthz為去質(zhì)子化的N-丁酰-2-喹啉甲酰肼;bzqnthz為去質(zhì)子化的N-苯甲酰-2-喹啉甲酰肼。)對上述14個晶體做了X-射線單晶衍射實驗,并對其結(jié)構(gòu)做了解析,結(jié)果表明,晶體2、3、4、5、7、8、9為三斜晶系,空間群為P-1;晶體1、6、11、12、13、14為單斜晶系,其中晶體1的空間群為P21/c,晶體6的空間群為P21/n,晶體11、12、14的空間群為C2/c,晶體13的空間群為I2/a;晶體10為正交晶系,空間群是Pnn2為非心空間群,flack=0.089(13)。所有的配合物均為單核配合物。晶體1、2、3、8為扭曲的四方錐配位構(gòu)型,由一個金屬離子、一個去氫配體和其他輔助配體構(gòu)成。晶體4、5、6、7、9、10、11、12、13、14配位方式都是扭曲的八面體配位構(gòu)型,結(jié)構(gòu)類似,都是由一個金屬離子與兩個去質(zhì)子配體螯合構(gòu)成,部分配合物分子還含有DMF分子。在14個晶體的晶胞中都存在著氫鍵相互作用從而使他們具有穩(wěn)定的晶體結(jié)構(gòu)。且分子與分子之間都可以構(gòu)成氫鍵環(huán),使得結(jié)構(gòu)可以在三維空間進一步擴張形成穩(wěn)定的晶體結(jié)構(gòu)。通過對14個晶體的紅外光譜數(shù)據(jù)分析得到,各個晶體的特定官能團峰值位置以及配體與金屬配位后峰值位置的變化。紫外和熒光性質(zhì)測試表明,配合物均是在紫外光下激發(fā),激發(fā)態(tài)的分子內(nèi)部鄰近的質(zhì)子給體與質(zhì)子受體之間的質(zhì)子發(fā)生轉(zhuǎn)移反應(yīng)。并且金屬離子的d軌道均與大環(huán)物質(zhì)的π鍵發(fā)生相互作用。在紫外光照射下,晶體1、2、3、4、8、11均發(fā)出黃光。對晶體3、4、5、6和配體Hpqnthz進行了量子化學計算和說明,可以得出其前線分子軌道的能量差值發(fā)生改變,這種變化關(guān)系與其性質(zhì)存在較好的對應(yīng)關(guān)系。
[Abstract]:In this paper, a series of unsymmetrical quinolinamide organic compounds were designed and synthesized by qualitative modification of carboxylic groups on nitrogen heterocycles using 2-quinoline carboxylic acid as parent. Fourteen different complexes were synthesized and their single crystals were obtained by the reaction of these heterocyclic derivatives with different metal salts. Their single crystal structure, infrared spectrum, ultraviolet spectrum, fluorescence spectrum and thermal spectrum were analyzed, and the quantum chemistry was calculated. The 14 crystals are [Pb (pqnthz) (OAc)] (1) [Pb (pqnthz) (NO_3 (H _ s _ 2O)] (2) [Cd (pqnthz) I (H _ s _ 2O] H _ (2). 2O (3) [Zn (pqnthz) _ 2] DMF (4) [Ni (pqnthz) _ 2] DMF (5) [Co (pqnthz) _ 2] (6) [Mn (pqnthz) _ 2] DMF (7) [Zn (bqnthz) Cl (CH_3OH] (8) [ Zn (bqnthz) _ 2] DMF (9) [Mn (bqnthz) _ 2] (10) [Zn (bzqnthz) _ 2] H _ 2O (11) [Mn (bzqnthz) _ 2] H _ 2O (12) [Co (bzqnthz) _ 2] (13) [Ni (bzqnthz) _ 2] 2] (14) (pqnthz is deprotonated N-propionyl-2-quinolinyl hydrazide; Bqnthz is deprotonated N-butyl-2-quinolinyl hydrazide and bzqnthz is de-protonated N-benzoyl-2-quinoline formyl hydrazide. The X-ray single crystal diffraction experiments were carried out on the 14 crystals mentioned above and their structures were analyzed. The results show that the crystal is triclinic system and space group is P-1. The space group of crystal 1 is P21 / c, the group of space of crystal 6 is P21 / n, the space group of crystal 111212N14 is C _ 2 / c, and the space group of crystal 13 is I _ 2 / a. The crystal 10 is an orthorhombic system, the space group is Pnn2 is a non-central space group, and flack=0.089 (13). All the complexes are mononuclear complexes. The crystal is a twisted tetragonal coordination configuration consisting of a metal ion, a dehydrogen ligand and other auxiliary ligands. The coordination modes of the crystals are all distorted octahedron coordination structures, which are composed of a metal ion chelating with two deprotonated ligands, and some of the complexes also contain DMF molecules. Hydrogen bond interaction exists in the crystal cell of 14 crystals, which makes them have stable crystal structure. The hydrogen bond ring can be formed between molecule and molecule, which makes the structure further expand in three dimensional space to form a stable crystal structure. By analyzing the infrared spectrum data of 14 crystals, the peak position of specific functional groups in each crystal and the change of peak position after ligand coordination with metal were obtained. UV and fluorescence measurements show that the complexes are excited under ultraviolet light, and the protons transfer reaction between the adjacent proton donor and the proton receptor occurs in the excited state. Moreover, the d orbitals of metal ions interact with 蟺 bonds of macrocyclic matter. Under UV irradiation, all crystals emit yellow light. The quantum chemical calculation and explanation of the crystal 3 + 4 + 5 + 5 + 6 and the ligand Hpqnthz show that the energy difference of its frontier molecular orbitals is changed, which has a good corresponding relationship with its properties.
【學位授予單位】：華僑大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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