Synthesis, Characterization and Properties of Two Coppper(Ⅱ) Complexes Derived from 4-Amino-2,6-Dimethoxypyrimidine

doi:10.16553/j.cnki.issn1000-985x.2024.0185

Abstract

Abstract: Two new copper(Ⅱ) complexes [Cu(amp)Lx](ClO₄)₂(x=1, 2) were synthesized by self-assemble of 4-amino-2,6-dimethoxypyrimidine(amp), organic polyamine N-(2-aminoethyl)-1,3-propylamine) (L1), (bi(3-aminopropyl)-amine (L2) and copper salt using the solvent method. The products were characterized by means of elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, powder X-ray diffraction, and scanning electron microscopy. The crystal structure of [Cu(amp)L2](ClO₄)₂ was analyzed by single crystal X-ray diffraction. The results indicates that [Cu(amp)L2](ClO₄)₂ belongs to monoclinic system, space group P2₁/c with a=1.207 90(12) nm, b=1.327 91(13) nm, c=1.390 39(14) nm, a=90°, b=90.056(3)°, γ=90°. In addition, the fluorescence spectrum shows that the ligand amp has an emission wavelength of 387 nm with a strong fluorescence value. However, when the amp coordinates with orgnic polyamines and copper to form a complex, significant fluorescence quenching occurs. This phenomenon indicates that amp interacting with the organic polyamines(L1, L2) have potential functions as fluorescent probes for copper ions. The antibacterial activity of the products in vitro were studied by agar plate diffusion method. The results show that the products have good antibacterial activity against the tested microorganisms.

Key words: 4-amino-2,6-dimethoxypyrimidine, organic polyamine, copper complex, fluorescent property, crystal structure, antibacterial activity

CLC Number:

O614.121

XU Tongtao, WAN Hongshan, YANG Tianxing, GAO Min, WANG Chong. Synthesis, Characterization and Properties of Two Coppper(Ⅱ) Complexes Derived from 4-Amino-2,6-Dimethoxypyrimidine[J]. Journal of Synthetic Crystals, 2025, 54(4): 684-692.

References

[1] 佟萍, 吴江萌, 徐萍, 等. 2-氨基吡啶类双核铜(Ⅱ)配合物的合成、晶体结构及性质[J]. 无机化学学报, 2022, 38(7): 1309-1316.
TONG P, WU J M, XU P, et al. Syntheses, crystal structures, and properties of binuclear copper(Ⅱ) complexes derived from 2-aminopyridines[J]. Chinese Journal of Inorganic Chemistry, 2022, 38(7): 1309-1316 (in Chinese).
[2] WANG L, WEI Z L, LIU C, et al. Synthesis and characterization for a highly selective bis(salamo)-based chemical sensor and imaging in living cell[J] . Spectrochim. Acta A, 2020, 239: 118496.
[3] KUMAR MUDI P, BANDOPADHYAY N, JOSHI M, et al. Schiff base triggering synthesis of copper(Ⅱ) complex and its catalytic fate towards mimics of phenoxazinone synthase activity[J]. Inorganica Chimica Acta, 2020, 505: 119468.
[4] 卜康, 吉玉如, 王楠, 等. 萘羧酸膦酸铜配合物的合成与表征[J]. 人工晶体学报, 2021, 50(1): 102-105.
BU K, JI Y R, WANG N, et al. Synthesis and characterization of copper naphthoic acid phosphonate[J]. Journal of Synthetic Crystals, 2021, 50(1): 102-105 (in Chinese).
[5] 代思玉, 刘宇奇, 李杨华, 等. 双配体配位的Ni(Ⅱ)、Cu(Ⅱ)金属配合物的结构和性能[J]. 人工晶体学报, 2021, 50(12): 2283-2292.
DAI S Y, LIU Y Q, LI Y H, et al. Structure and properties of Ni(Ⅱ) and Cu(Ⅱ) metal complexes coordinated by two ligands[J]. Journal of Synthetic Crystals, 2021, 50(12): 2283-2292 (in Chinese).
[6] 祁金阳, 党欣语, 张迎春, 等. 两种苯磺酸铜配合物的结构及催化性能研究[J]. 化学研究与应用, 2022, 34(11): 2610-2618.
QI J Y, DANG X Y, ZHANG Y C, et al. Study on the structure and catalytic property of two copper benzenesulfonate complexes[J]. Chemical Research and Application, 2022, 34(11): 2610-2618 (in Chinese).
[7] 林宏艳, 林佳凤, 田原, 等. 酰胺基配体构筑的两种铜配合物的组装、结构与催化性能[J]. 化学研究与应用, 2018, 30(5): 728-735.
LIN H Y, LIN J F, TIAN Y, et al. Two copper compounds constructed by the amide-based ligands: assembly, structure and catalytic properties[J]. Chemical Research and Application, 2018, 30(5): 728-735 (in Chinese).
[8] 郑长征, 杜筱笛, 权俐, 等. 2-呋喃甲醛水杨酰腙铜配合物的合成、晶体结构及抑菌活性[J]. 人工晶体学报, 2014, 43(9): 2434-2438.
ZHENG C Z, DU X D, QUAN L, et al. Synthesis, crystal structure and antibacterial activities of Cu(Ⅱ)complex with 2-furaldehyde salicylhydrazone hydrazone[J]. Journal of Synthetic Crystals, 2014, 43(9): 2434-2438 (in Chinese).
[9] 蔡戴宏, 莫慧雯, 何良, 等. 三元混配铜(Ⅱ)配合物的晶体结构、DNA作用及其生物活性[J]. 无机化学学报, 2021, 37(1): 74-84.
CAI D H, MO H W, HE L, et al. Crystal structure, DNA binding properties and biological activities of a ternary mixed-ligand copper (Ⅱ) complex[J]. Chinese Journal of Inorganic Chemistry, 2021, 37(1): 74-84 (in Chinese).
[10] 曾振芳, 袁芳, 黄秋萍, 等. 对氯苯甲酸构筑的铜(Ⅱ)配合物的合成、HSA结合及细胞毒性[J]. 人工晶体学报, 2022, 51(1): 126-131.
ZENG Z F, YUAN F, HUANG Q P, et al. Synthesis, HSA binding, and cytotoxic activity of copper(Ⅱ) complex constructed by p-chlorobenzoic acid[J]. Journal of Synthetic Crystals, 2022, 51(1): 126-131 (in Chinese).
[11] 曾振芳, 蔡杰慧, 黄秋萍, 等. 铜(Ⅱ)配合物{[Cu(OMBA)₂]₂·(DMF)₂}的合成、CT-DNA结合及细胞毒性[J]. 人工晶体学报, 2021, 50(12): 2300-2306.
ZENG Z F, CAI J H, HUANG Q P, et al. Synthesis, CT-DNA binding, and cytotoxic activity of copper(Ⅱ) complex{[Cu(OMBA)₂]₂·(DMF)₂}[J]. Journal of Synthetic Crystals, 2021, 50(12): 2300-2306 (in Chinese).
[12] CHAI L Q, LI Y X, CGEN L C, et al. Synthesis, X-ray Structure, spectroscopic, electrochemical Properties and DFT calculation of a bridged ainuclear copper(Ⅱ) complex[J]. Inorganica Chimica Acta, 2016, 444: 193-201.
[13] 佟萍, 刘泽含, 徐达峰, 等. Schiff 碱及其金属配合物在医药领域应用进展[J]. 化学研究与应用, 2022, 34(6): 1233-1241.
TONG P, LIU Z H, XU D F, et al. Application progress of Schiff bases and their metal complexes in medicine field[J]. Chemical Research and Application, 2022, 34(6): 1233-1241 (in Chinese).
[14] GEETH VINCENT S, JOSEPH J. Evaluation of antioxidant activity and antimalarial activity of flavone based tetradentate ligand and its metal complexes[J]. Materials Today: Proceedings, 2021, 45: 2159-2165.
[15] LIU R X, WANG C Y, WU Y S, et al. The copper(Ⅱ) complexes of new anthrahydrazone ligands: in vitro and in vivo antitumor activity and structure-activity relationship[J]. Journal of Inorganic Biochemistry, 2020, 212: 111208.
[16] 许同桃. 丹皮酚、有机多胺衍生物及其金属配合物的合成、结构及生物活性研究[D]. 南京: 南京理工大学, 2007.
XU T T. Synthesis, structure and biological activity of paeonol, organic polyamine derivatives and their metal complexes[D]. Nanjing: Nanjing University of Science and Technology, 2007 (in Chinese).
[17] XU T T, GAO J, XU X Y, et al. Synthesis and crystal structure of a new ternary mixed ligand complex[Cu(ampym)(bapa)Cl](ClO₄) (ampym=2-Aminopyrimidine, bapa = Bi(3-aminopropyl)amine)[J]. Chinese Journal of Structural Chemistry, 2006, 25(4): 469-472.
[18] XU X Y, XU T T, GAO J, et al. Synthesis, crystal structure and properties of a new mixed ligand copper(Ⅱ) complex[Cu(imH) (aepa)](ClO₄)₂ (imH=imidazole, aepa=N-(2-aminoethyl)-1, 3-propylamine)[J]. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2006, 36(9): 681-686.
[19] 罗劲, 何凌惠, 聂会祥, 等. 新型含1, 2, 4-三唑的嘧啶衍生物的合成与生物活性[J]. 农药, 2023, 62(4): 244-251.
LUO J, HE L H, NIE H X, et al. Synthesis and biological activities of novel pyrimidine derivatives containing 1, 2, 4-triazole[J]. Agrochemicals, 2023, 62(4): 244-251 (in Chinese).
[20] 肖俊丽, 骆荣双, 刘钊, 等. 4-氯-2-甲基吡啶并[3, 2-d]嘧啶的合成[J]. 化学研究与应用, 2022, 34(2): 444-448.
XIAO J L, LUO R S, LIU Z, et al. Synthesis of 4-chloro-2-methylpyrido[3, 2-d]pyrimidine[J]. Chemical Research and Application, 2022, 34(2): 444-448 (in Chinese).
[21] 张楠, 姚世博, 任瑞, 等. 4-氨基嘧啶并[4, 5-D]嘧啶Cu(Ⅱ)配合物的合成、结构和荧光性质[J]. 天津师范大学学报(自然科学版), 2021, 41(3): 24-28.
ZHANG N, YAO S B, REN R, et al. A new copper(Ⅱ) complex based on 4-aminopyrimido[4, 5-D]pyrimidine: synthesis, structure and luminescence property[J]. Journal of Tianjin Normal University (Natural Science Edition), 2021, 41(3): 24-28 (in Chinese).
[22] 吴军, 孙燕萍, 张培志, 等. 取代嘧啶化合物的合成和生物活性研究[J]. 有机化学, 2004, 24(11): 1403-1406.
WU J, SUN Y P, ZHANG P Z, et al. Synthesis and biological activity of substituted pyrimidine derivatives[J]. Chinese Journal of Organic Chemistry, 2004, 24(11): 1403-1406 (in Chinese).
[23] IFTIKHAR B, JAVED K, KHAN M S U, et al. Synthesis, characterization and biological assay of Salicylaldehyde schiff Base Cu (Ⅱ) complexes and their precursors[J]. Journal of Molecular Structure, 2018, 1155: 337-348.
[24] SHELDRICK G M. SHELXS-97: Program for crystal structure determination[CP]. University of Gottingen, Germany, 1997.
[25] 许同桃, 高健. 丹皮酚缩脂肪胺Schiff碱的合成及生物活性研究[J]. 化学试剂, 2012, 34(9): 849-852.
XU T T, GAO J. Synthesis, characterization and biological activity of the Schiff base compound from paeonol and organic polyamine[J]. Chemical Reagents, 2012, 34(9): 849-852 (in Chinese).
[26] LIN S K, MARCH J. March’s advanced organic chemistry: reactions, mechanisms, and structure, 5th edition[J]. Molecules, 2001, 6(12): 1064-1065.
[27] 邓彦, 阎平轩, 赵曼, 等. 氮杂环卡宾Cu配合物的制备及荧光猝灭性质[J]. 沈阳化工大学学报, 2022, 36(1): 6-10.
DENG Y, YAN P X, ZHAO M, et al. Preparation and fluorescence quenching properties of nitrogen heterocarbene Cu complexes[J]. Journal of Shenyang University of Chemical Technology, 2022, 36(1): 6-10 (in Chinese).
[28] 李永强, 王金中, 王崇妍, 等. 水杨醛缩氨基硫脲-铜荧光猝灭反应的研究及应用[J]. 分析测试学报, 2007, 26(2): 232-234.
LI Y Q, WANG J Z, WANG C Y, et al. Studies on fluorimetric quenching reaction between cupric ion and salicylic aldehyde thiosemicarbazone[J]. Journal of Instrumental Analysis, 2007, 26(2): 232-234 (in Chinese).
[29] IMRAN S, TAHA M, ISMAIL N H, et al. Synthesis of novel bisindolylmethane Schiff bases and their antibacterial activity[J]. Molecules, 2014, 19(8): 11722-11740.