Citation: Zhong-Xue LONG, Wei LI, Dong-Fang LI, Jia-Hui JING, Shan-Shan LIU. Synthesis, crystal structure, luminescence, and density functional theory calculation of rare earth complexes based on 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(3): 385-394. doi: 10.11862/CJIC.2023.009 shu

Synthesis, crystal structure, luminescence, and density functional theory calculation of rare earth complexes based on 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone

Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Corresponding author: Shan-Shan LIU, liushanshan2015@bipt.edu.cn
Received Date: 5 July 2022
Revised Date: 20 December 2022

Figures(7)

A series of mononuclear rare earth complexes [Ln(pmbp)₃(dmbipy)]·C₂H₅OH, where Ln=Tb (1-Tb), Ho (1-Ho), Er (1-Er) and Tm (1-Tm), were synthesized by using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone (Hpmbp) and 4,4'-dimethyl-2,2'-bipyridine (dmbipy) as ligands. Structure characterizations show that the complex is composed of one Ln³⁺ ion, three pmbp^-ions, one dmbipy molecule, and one free ethanol molecule, yielding the [LnO₆N₂] type structure. The continuous shape measurement (CShM) analyses show that the Ln³⁺ centers exhibit a distorted triangular dodecahedral geometry. Luminescence measurements showed that all of the complexes exhibit characteristic emission peaks of the corresponding rare earth ions. And it was found that the ligand could sensitize Ho³⁺ and Er³⁺ well, while the sensitization of Tb³⁺ and Tm³⁺ was weak. In addition, the HOMO and LUMO of Hpmbp ligands, dmbipy ligands, and rare earth complexes were calculated and analyzed by the density functional theory method. It is found that for Tb, Ho, and Tm complexes with an odd number of electrons in the center metal atom, the bond lengths between metal ions and coordination atoms are shorter with the increasing number of electrons in metal ions, while the bond lengths of Er—O and Er—N of 1-Er are between those of 1-Ho and 1-Tm. For 1-Tb, 1-Ho, and 1-Tm, the orbital energy of HOMO and LUMO decreases with increasing electron number, which is consistent with the rule of bond length. For 1-Tb, 1-Ho and 1-Er, the HOMO-LUMO gap increases with the increase of electron number. In addition, the HOMO-LUMO energy gaps of the four complexes are lower than that of the ligands.
- 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone,
- rare earth complex,
- luminescence,
- density functional theory calculation
1. [1]
  Shang K X, He W T, Sun J, Hu D C. Synthesis, crystal structure and near-infrared luminescence of rare earth metal (Y^Ⅲ, Er^Ⅲ, Ho^Ⅲ) complexes containing semirigid tricarboxylic acid ligand[J]. J. Mol. Struct., 2021,1246131097. doi: 10.1016/j.molstruc.2021.131097
2. [2]
  Kovacs T A, Felinto M C F C, Paolini T B, Ali B, Nakamura L K O, Teotonio E E S, Brito H F, Malta O L. Synthesis and photoluminescence properties of [Eu(dbm)₃·PX] and[Eu(acac)₃·PX] complexes[J]. J. Lumin., 2018,193:98-105. doi: 10.1016/j.jlumin.2017.09.029
3. [3]
  Ilmi R, Iftikhar K. Photophysical properties of lanthanide (Ⅲ) 1,1,1-trifluoro-2,4-pentanedione complexes with 2,2'-bipyridyl: An experimental and theoretical investigation[J]. J. Photochem. Photobiol. A-Chem., 2017,333:142-155. doi: 10.1016/j.jphotochem.2016.10.014
4. [4]
  Zahariev T, Shandurkov D, Gutzov S, Trendafilova N, Enseling D, Justel T, Georgieva I. Phenanthroline chromophore as efficient antenna for Tb³⁺ green luminescence: A theoretical study[J]. Dyes Pigment., 2021,185108890. doi: 10.1016/j.dyepig.2020.108890
5. [5]
  Cai L L, Hu Y T, Li Y, Wang K, Zhang X Q, Muller G, Li X M. Solid-state luminescence properties, Hirshfeld surface analysis and DFT calculations of mononuclear lanthanide complexes (Ln=Eu^Ⅲ, Gd^Ⅲ, Tb^Ⅲ, Dy^Ⅲ) containing 4'-phenyl-2,2': 6',2''-terpyridine[J]. Inorg. Chim. Acta, 2019,489:85-92. doi: 10.1016/j.ica.2019.02.001
6. [6]
  Luo Y M, Li J, Xiao L X, Tang R R, Tang X C. Synthesis, characterization and fluorescence properties of Eu(Ⅲ) and Tb(Ⅲ) complexes with novel mono-substituted β-diketone ligands and 1,10-phenanthroline[J]. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 2009,72(4):703-708. doi: 10.1016/j.saa.2008.10.059
7. [7]
  Yan B, Zhou B. Photophysical properties of dysprosium complexes with aromatic carboxylic acids by molecular spectroscopy[J]. J. Photochem. Photobiol. A-Chem., 2005,171(2):181-186. doi: 10.1016/j.jphotochem.2004.10.012
8. [8]
  Wang Q M, Yan B, Zhang X H. Photophysical properties of novel lanthanide complexes with long chain mono-eicosyl cis-butene dicarboxylate[J]. J. Photochem. Photobiol. A-Chem., 2005,174(2):119-124. doi: 10.1016/j.jphotochem.2005.02.016
9. [9]
  Jia J H, Li Q W, Chen Y C, Liu J L, Tong M L. Luminescent single-molecule magnets based on lanthanides: Design strategies, recent advances and magneto-luminescent studies[J]. Coord. Chem. Rev., 2019,378:365-381. doi: 10.1016/j.ccr.2017.11.012
10. [10]
  De Silva C R, Li F Y, Huang C H, Zheng Z P. Europium β-diketonates for red-emitting electroluminescent devices[J]. Thin Solid Films, 2008,517(2):957-962. doi: 10.1016/j.tsf.2008.08.118
11. [11]
  Yan B, Zhou B. Two photoactive lanthanide (Eu³⁺, Tb³⁺) hybrid materials of modified β-diketone bridge directly covalently bonded mesoporous host (MCM-41)[J]. J. Photochem. Photobiol. A-Chem., 2008,195:314-322. doi: 10.1016/j.jphotochem.2007.10.019
12. [12]
  Albrecht M, Schmid S, Dehn S, Wickleder C, Zhang S, Bassett A P, Pikramenou Z, Frohilch C. Diastereoselective formation of luminescent dinuclear lanthanide (Ⅲ) helicates with enantiomerically pure tartaric acid derived bis (β-diketonate) ligands[J]. New J. Chem., 2007,31(10):1755-1762. doi: 10.1039/b705090a
13. [13]
  Mello Donega C, Junior S A, Sa G F. Europium (Ⅲ) mixed complexes with β-diketones and o-phenanthroline-N-oxide as promising light-conversion molecular devices[J]. Chem. Commun., 1996,10:1199-1200.
14. [14]
  Bellusci A, Barberio G, Crispini A, Ghedini M, Deda M L, Pucci D. Synthesis and luminescent properties of novel lanthanide (Ⅲ) β-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands[J]. Inorg. Chem., 2005,44:1818-1825. doi: 10.1021/ic048951r
15. [15]
  Chen X Y, Yang X P, Holliday B J. Metal-controlled assembly of near-infrared-emitting pentanuclear lanthanide β-diketone clusters[J]. J. Inorg. Chem., 2010,49(6):2583-2585. doi: 10.1021/ic902513z
16. [16]
  QIU Y N, SUN L N, LIU T, LIU Z, SHI L Y, YAN W. Recent advances in near-infrared luminescent lanthanide complexes and hybrid materials[J]. Journal of the Chinese Society of Rare Earths, 2012,30(2):129-145.
17. [17]
  ZHONG G L, YANG K Z, FENG Y, ZHU G Y. Research on the Langmuir-Blodgett films of rare earth-β-diketone complexes and triplet energy transfer[J]. Chem. J. Chinese Universities, 1997,18(7):1194-1196. doi: 10.3321/j.issn:0251-0790.1997.07.042
18. [18]
  King D T, Worrall L J, Gruninger R, Strynadka N C J. New Delhi metallo-β-lactamase: Structural insights into β-lactam recognition and inhibition[J]. J. Am. Chem. Soc., 2012,134(28):11362-11365. doi: 10.1021/ja303579d
19. [19]
  CHENG N N. Synthesis, characterization and biological activity of ternary rare earth complexes with β-diketone and heterocycle. Shanghai: Shanghai Normal University, 2012.
20. [20]
  HUANG L, HUANG C H. Study on photoluminescence and electroluminescence of the rare earth complexes[J]. Acta Chim. Sinica, 2000,58(12):1493-1498. doi: 10.3321/j.issn:0567-7351.2000.12.002
21. [21]
  Zhao J Y, Ren N, Zhang J J. Supramolecular of lanthanide-2,6-di-methylbenzoic acid-2,2': 6',2''-terpyridine materials: Crystal structures, luminescent property, and thermochemical behaviour[J]. Polyhedron, 2021,194114892. doi: 10.1016/j.poly.2020.114892
22. [22]
  Wang D J, Liu H, Fan L, Yin G D, Hu Y J, Zheng J. Synthesis and photoluminescent behavior of Eu(Ⅲ) complexes with 4,4,4-trifluoro-1-(6-methoxy-naphthalen-2-yl)-butane-1,3-dione[J]. Synth. Met., 2015,209:267-272. doi: 10.1016/j.synthmet.2015.08.002
23. [23]
  Chu Y, Hao H X, Xie H D, Chen C L, Cai P Q, Seo H J. Preparation of lanthanide (Eu³⁺, Tb³⁺)-complex-grafted copolymer of methyl methacrylate and maleic anhydride films and the promising application as LED luminous layers[J]. J. Mater. Sci.-Mater. Electron., 2016,28:5615-5622.
24. [24]
  JING J H, LIU B, MENG Y S, ZHANG Y Q, LU H Q, LIU S S. Crystal structure, magnetic properties and theoretical investigation of a dysprosium (The original text is dysprsoium) complex based on 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one[J]. Chinese J. Inorg. Chem., 2021,37(4):623-628.
25. [25]
  Liu B, Jin H, Kuang Z A, Chen X, Meng Y S, Lin S J, Liu S S. Bifunctional sulfur-ligated erbium complex: Crystal structure, magnetic and luminescent properties[J]. Inorg. Chim. Acta, 2020,501119297. doi: 10.1016/j.ica.2019.119297
26. [26]
  Sheldrick G M. SHELXTL-Integrated space-group and crystal structure determination[J]. Acta Crystallogr. Sect. A, 2015,A71:3-8.
27. [27]
  Sheldrick G M. SHELXL-2018. University of Göttingen, Germany, 2018.
28. [28]
  Alvarez S, Alemany P, Casanova D, Cirera J, Llunell M, Avnir D. Shape maps and polyhedral interconversion paths in transition metal chemistry[J]. Coord. Chem. Rev., 2005,249:1693-1708. doi: 10.1016/j.ccr.2005.03.031
29. [29]
  Shen C Q, Yan T L, Wang Y T, Ye Z J, Xu C J, Zhou W J. Synthesis, structure and luminescence properties of binary and ternary complexes of lanthanide (Eu³⁺, Sm³⁺ and Tb³⁺) with salicylic acid and 1,10-phenanthroline[J]. J. Lumin., 2017,184:48-54. doi: 10.1016/j.jlumin.2016.12.018
30. [30]
  Liu S S, Liu B, Ding M M, Meng Y S, Jing J H, Zhang Y Q, Wang X C, Lin S J. Substituent effects of auxiliary ligand in mononuclear dibenzoylmethane Dy^Ⅲ/Er^Ⅲ complexes: Single-molecule magnetic behavior and luminescence properties[J]. CrystEngComm, 2020,22(45):7929-7934. doi: 10.1039/D0CE01147A
1. [1]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
2. [2]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
3. [3]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
4. [4]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
5. [5]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
6. [6]
  Feng Lu , Tao Wang , Qi Wang . Preparation and Characterization of Water-Soluble Silver Nanoclusters: A New Design and Teaching Practice in Materials Chemistry Experiment. University Chemistry, 2025, 40(4): 375-381. doi: 10.12461/PKU.DXHX202406005
7. [7]
  YanYuan Jia , Rong Rong , Jie Liu , Jing Guo , GuoYu Jiang , Shuo Guo . Unity is Strength, and Independence Shines: A Science Popularization Experiment on AIE and ACQ Effects. University Chemistry, 2024, 39(9): 349-358. doi: 10.12461/PKU.DXHX202402035
8. [8]
  Qin Li , Kexin Yang , Qinglin Yang , Xiangjin Zhu , Xiaole Han , Tao Huang . Illuminating Chlorophyll: Innovative Chemistry Popularization Experiment. University Chemistry, 2024, 39(9): 359-368. doi: 10.3866/PKU.DXHX202309059
9. [9]
  Zehua Zhang , Haitao Yu , Yanyu Qi . 多重共振TADF分子的设计策略. Acta Physico-Chimica Sinica, 2025, 41(1): 2309042-. doi: 10.3866/PKU.WHXB202309042
10. [10]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
11. [11]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
12. [12]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
13. [13]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
14. [14]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
15. [15]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
16. [16]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
17. [17]
  Yan ZHAO , Xiaokang JIANG , Zhonghui LI , Jiaxu WANG , Hengwei ZHOU , Hai GUO . Preparation and fluorescence properties of Eu³⁺-doped CaLaGaO₄ red-emitting phosphors. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1861-1868. doi: 10.11862/CJIC.20240242
18. [18]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
19. [19]
  Shuwen SUN , Gaofeng WANG . Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 613-620. doi: 10.11862/CJIC.20230368
20. [20]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(1301)
HTML views(154)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142