Synthesis, Crystal Structure, and Luminescence Properties of Eu (III)  Complex with Two Pyridinedicarboxylic Acids

Abstract

Abstract: A new Eu(III) complex {[Eu₂(3,5-pdc)(3,4-pdc)₂(H₂O)₄]·3H₂O}_n was synthesized by reacting 3,5-pyridinedioic acid (3,5-H₂pdc) and 3,4-pyridinedioic acid (3,4-H₂pdc) with Eu(ClO₄)₃ water solution at 170 ℃ by hydrothermal method. X-ray single crystal diffraction shows that the complex is a two-dimensional structure. The complex crystallized in monoclinic crystal system and P2₁/m space group. Its crystal cell parameters are a=0.598 20(4) nm,b=2.639 21(19) nm, c=1.147 58(9) nm, α=γ=90°,β=102.628 0(10)°. The complex was characterized by elemental analysis, infrared spectroscopy. The excitation and emission spectrum, fluorescence lifetime and luminescence quantum yield of the complex were tested. The results indicate that the complex can emit characteristic spectra of Eu (III). The fluorescence lifetime of ⁵D₀→⁷F₂ transition is 338 μs, and the absolute luminescence quantum yield is 24% under the excitation of 313 nm ultraviolet light.

Key words: 3,5-pyridyldicarboxylic acid, 3,4-pyridinedicarboxylic acid, europium complex, hydrothermal method, crystal structure, photoluminescence, quantum yield

CLC Number:

O641.4

WANG Hongsheng, LI Hui, LIU Zhan, LIANG Cailian. Synthesis, Crystal Structure, and Luminescence Properties of Eu (III) Complex with Two Pyridinedicarboxylic Acids[J]. Journal of Synthetic Crystals, 2023, 52(10): 1829-1835.

References

[1] GAI Y L, GUO Q, XIONG K C, et al. Mixed-lanthanide metal-organic frameworks with tunable color and white light emission[J]. Crystal Growth & Design, 2017, 17(3): 940-944.
[2] LIU T, YU Y H, ZHANG H Z, et al. Syntheses and structures of four pairs of coordination polymers based on 2, 2’-((5-(methoxycarbonyl)-1, 3-phenylene)bis(oxy)) dipropanoic acid[J]. Crystal Growth & Design, 2017, 17(4): 1788-1795.
[3] 王宏胜, 李公春, 张万强, 等. 两种吡啶多羧酸与稀土Eu(Ⅲ)配合物的结构与光致发光性质[J]. 人工晶体学报, 2017, 46(1): 168-173.
WANG H S, LI G C, ZHANG W Q, et al. Structure and photoluminescence properties of a Eu(Ⅲ) complex with two ligands of mixed pyridinecarboxylic acid[J]. Journal of Synthetic Crystals, 2017, 46(1): 168-173 (in Chinese).
[4] WANG M M, MENG X X, HAN Z S, et al. Synthesis, crystal structure, and magnetization dynamics of phenoxy-bridged Dy₂ complexes with different counter anions and lattice solvents[J]. Crystal Growth & Design, 2023, 23(5): 3651-3659.
[5] ZHANG S W, SHI W, LI L L, et al. Lanthanide coordination polymers with “fsy-type” topology based on 4, 4’-azobenzoic acid: syntheses, crystal structures, and magnetic properties[J]. Inorganic Chemistry, 2014, 53(19): 10340-10346.
[6] LIU C M, ZHANG D Q, ZHU D B. A 3D MOF constructed from dysprosium(III) oxalate and capping ligands: ferromagnetic coupling and field-induced two-step magnetic relaxation[J]. Chemical Communications, 2016, 52(26): 4804-4807.
[7] CHEN D M, ZHANG X P, SHI W, et al. Microporous metal-organic framework based on a bifunctional linker for selective sorption of CO₂ over N₂ and CH₄[J]. Inorganic Chemistry, 2015, 54(11): 5512-5518.
[8] MA S Q, YUAN D Q, WANG X S, et al. Microporous lanthanide metal-organic frameworks containing coordinatively linked interpenetration: syntheses, gas adsorption studies, thermal stability analysis, and photoluminescence investigation[J]. Inorganic Chemistry, 2009, 48(5): 2072-2077.
[9] SONG T Q, DONG J, YANG A F, et al. Wheel-like Ln₁₈ cluster organic frameworks for magnetic refrigeration and conversion of CO₂[J]. Inorganic Chemistry, 2018, 57(6): 3144-3150.
[10] D’VRIES R F, SNEJKO N, IGLESIAS M, et al. Ln-MOF pseudo-merohedral twinned crystalline family as solvent-free heterogeneous catalysts[J]. Crystal Growth & Design, 2014, 14(5): 2516-2521.
[11] WANG J, WANG J R, LI Y, et al. A europium(iii)-based metal-organic framework as a naked-eye and fast response luminescence sensor for acetone and ferric iron[J]. New Journal of Chemistry, 2016, 40(10): 8600-8606.
[12] YAN W, ZHANG C L, CHEN S G, et al. Two lanthanide metal-organic frameworks as remarkably selective and sensitive bifunctional luminescence sensor for metal ions and small organic molecules[J]. ACS Applied Materials & Interfaces, 2017, 9(2): 1629-1634.
[13] 何睿夫, 周非凡, 屈军乐, 等. 金属有机框架材料在有机钙钛矿太阳能电池中的应用进展[J]. 发光学报, 2021, 42(11): 1722-1738.
HE R F, ZHOU F F, QU J L, et al. Research progress of metal-organic frameworks in organic perovskite solar cells[J]. Chinese Journal of Luminescence, 2021, 42(11): 1722-1738 (in Chinese).
[14] SATPUTE N S, MEHARE C M, TIWARI A, et al. Synthesis and luminescence characterization of downconversion and downshifting phosphor for efficiency enhancement of solar cells: perspectives and challenges[J]. ACS Applied Electronic Materials, 2022, 4(7): 3354-3391.
[15] MARTN-RAMOS P, SILVA M R, COYA C, et al. Novel erbium(iii) fluorinated β-diketonate complexes with N, N-donors for optoelectronics: from synthesis to solution-processed devices[J]. Journal of Materials Chemistry C, 2013, 1(15): 2725-2734.
[16] 于笑寒, 王宏胜, 韩春杰,等. 二维配位聚合物[Tb(1,4-bdc)_1.5(phen)(H₂O)]_n的结构与光致发光性能研究[J].人工晶体学报, 2019, 48(6): 1055-1059.
YU X H, WANG H S, HAN C J, et al. Crystal structure and luminescent properties of 2D coordination polymer [Tb(1,4-bdc)_1.5(phen)(H₂O)]_n[J]. Journal of Synthetic Crystals, 2019, 48(6): 1055-1059 (in Chinese).
[17] ZHAO Q Q, ZHU M M, REN N, et al. A series of novel lanthanide complexes with 2-bromine-5-methoxybenzoic acid and 2, 2’-bipyridine: syntheses, crystal structures, and luminescent properties[J]. Journal of Molecular Structure, 2017, 1149: 171-182.
[18] SENGAR M, NARULA A K. Luminescence sensitization of Eu(III) complexes with aromatic schiff base and N, N’-donor heterocyclic ligands: synthesis, luminescent properties and energy transfer[J]. Journal of Fluorescence, 2019, 29(1): 111-120.
[19] WANG F F, YAN B. Intramolecular energy transfer and luminescence enhancement effect in inert rare earth ions (La, Y, Gd)-Eu³⁺ (Tb³⁺) co-fabricated organic-inorganic hybrid materials by covalent grafting[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2008, 194(2/3): 238-246.
[20] BUCZKO K, KARBOWIAK M. Co-fluorescence enhanced tuneable emission of lanthanide β-diketonate complexes in solid thin films[J]. Journal of Luminescence, 2013, 136: 130-140.
[21] YANG Q Y, PAN M, WEI S C, et al. Linear dependence of photoluminescence in mixed ln-MOFs for color tunability and barcode application[J]. Inorganic Chemistry, 2015, 54(12): 5707-5716.
[22] 周明明, 刘威, 杨成祥, 等. 多核稀土离子掺杂有机配合物转光剂的制备与应用[J]. 复合材料学报, 2023, 40(4): 2131-2139.
ZHOU M M, LIU W, YANG C X, et al. Preparation and application of multinuclear rare earth ion doped organic complex light conversion agents[J]. Acta Materiae Compositae Sinica, 2023, 40(4): 2131-2139 (in Chinese).
[23] SHELDRICK G M. SHELXS-97, program for crystal structure solution[U]. University of Gǒttingen, Germany, 1997.
[24] WANG H S, WANG S C, LI H, et al. Syntheses, structures and luminescent properties of Eu- and Tb-MOFs with 3, 5-pyridinedicarboxylate and 1, 2-benzenedicarboxylate[J]. Journal of Fluorescence, 2021, 31(5): 1393-1399.
[25] YANG A H, GAO H L, CUI J Z, et al. Syntheses, structures, and photoluminescence of lanthanide coordination polymers with pyridine-2, 3, 5, 6-tetracarboxylic acid[J]. CrystEngComm, 2011, 13(6): 1870-1876.
[26] 李小俊, 胡克良, 黄允兰, 等. 红外光谱对碱土金属二元羧酸盐结构的研究[J]. 光谱学与光谱分析, 2002, 22(3): 392-395.
LI X J, HU K L, HUANG Y L, et al. IR spectra of dicarboxylate of alkali-earth metal[J]. Spectroscopy and Spectral Analysis, 2002, 22(3): 392-395 (in Chinese).
[27] 孙聚堂, 王东利, 张克立, 等. 邻苯二甲酸锌配合物的合成、红外光谱和晶体结构[J]. 应用化学, 1997, 14(5): 98-100.
SUN J T, WANG D L, ZHANG K L, et al. Synthesis, infrared spectra and crystal structures of zinc phthalate complexes[J]. Chinese Journal of Applied Chemistry, 1997, 14(5): 98-100 (in Chinese).
[28] 洪广言. 稀土发光材料: 基础与应用[M]. 北京: 科学出版社, 2011.
HONG G Y. Rare earth luminescent materials-Fundamentals and applications[M]. Beijing: Science Press, 2011 (in Chinese).

Synthesis, Crystal Structure, and Luminescence Properties of Eu (III) Complex with Two Pyridinedicarboxylic Acids

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