喹啉酰胺配合物的合成、晶体结构与光学性质研究
发布时间：2019-01-29 20:41
【摘要】：本文选择2-喹啉羧酸为母体,通过对氮杂环上的羧酸基团的定性改造,设计合成出了一系列具有不对称结构的单边喹啉酰胺类有机化合物,并将这类氮杂环衍生物与不同的金属盐反应,合成出了14种不同的配合物并得到了其单晶。通过对它们的单晶结构、红外光谱、紫外光谱、荧光光谱以及热谱的分析,以及进行了量子化学的计算,来探索它们的晶体结构和光学性质。14个晶体分别为:[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为去质子化的N-丙酰-2-喹啉甲酰肼;bqnthz为去质子化的N-丁酰-2-喹啉甲酰肼;bzqnthz为去质子化的N-苯甲酰-2-喹啉甲酰肼。)对上述14个晶体做了X-射线单晶衍射实验,并对其结构做了解析,结果表明,晶体2、3、4、5、7、8、9为三斜晶系,空间群为P-1;晶体1、6、11、12、13、14为单斜晶系,其中晶体1的空间群为P21/c,晶体6的空间群为P21/n,晶体11、12、14的空间群为C2/c,晶体13的空间群为I2/a;晶体10为正交晶系,空间群是Pnn2为非心空间群,flack=0.089(13)。所有的配合物均为单核配合物。晶体1、2、3、8为扭曲的四方锥配位构型,由一个金属离子、一个去氢配体和其他辅助配体构成。晶体4、5、6、7、9、10、11、12、13、14配位方式都是扭曲的八面体配位构型,结构类似,都是由一个金属离子与两个去质子配体螯合构成,部分配合物分子还含有DMF分子。在14个晶体的晶胞中都存在着氢键相互作用从而使他们具有稳定的晶体结构。且分子与分子之间都可以构成氢键环,使得结构可以在三维空间进一步扩张形成稳定的晶体结构。通过对14个晶体的红外光谱数据分析得到,各个晶体的特定官能团峰值位置以及配体与金属配位后峰值位置的变化。紫外和荧光性质测试表明,配合物均是在紫外光下激发,激发态的分子内部邻近的质子给体与质子受体之间的质子发生转移反应。并且金属离子的d轨道均与大环物质的π键发生相互作用。在紫外光照射下,晶体1、2、3、4、8、11均发出黄光。对晶体3、4、5、6和配体Hpqnthz进行了量子化学计算和说明,可以得出其前线分子轨道的能量差值发生改变,这种变化关系与其性质存在较好的对应关系。
[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.
【学位授予单位】：华侨大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
[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.
【学位授予单位】：华侨大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
【相似文献】
相关期刊论文 前10条
1 林永华,胡宁海,周清廉,史恩栋,王明义,刘书珍,武士学;五磷酸铒的晶体结构[J];科学通报;1982年05期
2 林永华,胡宁海,周清廉,史恩栋,王明义,刘书珍,武士学;五磷酸铒的晶体结构[J];科学通报;1982年18期
3 杨先发;晶体结构模型的介绍[J];河北师范大学学报;1994年03期
4 李运伦;提高晶体结构教学质量的探索──试将内容分作两个层次讲授[J];湘潭师范学院学报(社会科学版);1998年03期
5 宓锦校,赵景泰,毛少瑜,黄种乐,黄雅熙,梁军,沈今川;动态三维真彩色晶体结构绘画系统的设计[J];计算机与应用化学;2000年04期
6 蔡金万,黄金陵,陈耐生,王俊东;1,4,8,11,15,18,22,25-八丁烷氧基酞菁铜的晶体结构[J];科学通报;2002年02期
7 吴茂英;金属皂的晶体结构[J];化学研究与应用;2003年03期
8 林树坤,陈昱,洪茂椿;软X射线分光晶体马来酸氢十六酯晶体结构及衍射性能[J];结构化学;2003年01期
9 陈雄斌,宋玉梅,熊仁根,游效曾;3-氨基-酪氨酸盐酸盐的合成与晶体结构(英文)[J];无机化学学报;2004年12期
10 姜隆;卢文贯;冯小龙;向华;鲁统部;;大环金属铜(Ⅱ)、镍(Ⅱ)配合物的模板合成与晶体结构[J];无机化学学报;2006年03期
相关会议论文 前10条
1 魏增斌;魏西莲;傅式洲;尹宝霖;;季胺盐型表面活性液的晶体结构与性能研究[A];中国化学会第十二届胶体与界面化学会议论文摘要集[C];2009年
2 田旭霞;高清环;刘延成;陈振锋;;鹅掌楸碱铜(Ⅰ)配合物的晶体结构[A];中国化学会第27届学术年会第03分会场摘要集[C];2010年
3 张景强;叶巧真;卢p樣，
本文编号：2417844
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2417844.html
教材专著
