Citation: Chuanbing HOU, Yingyu LI, Jingyi CHI, Yan DING, Zhiqiang WANG, Hongliang HAN, Xingru LI, Qionghua JIN. Synthesis, physicochemical properties and terahertz time domain spectroscopy of two lanthanide (Eu, Tb) bisphosphonate complexes containing keggin polyoxometalates[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(1): 135-144. doi: 10.11862/CJIC.20230394 shu

Synthesis, physicochemical properties and terahertz time domain spectroscopy of two lanthanide (Eu, Tb) bisphosphonate complexes containing keggin polyoxometalates

Chuanbing HOU ^{1, 2} ,
Yingyu LI ² ,
Jingyi CHI ² ,
Yan DING ² ,
Zhiqiang WANG ² ,
Hongliang HAN ² ,
Xingru LI ^{1, 2} ,
Qionghua JIN ^{2, 3, 4, 5,,}

1.
School of Resources, Environment and Tourism, Capital Normal University, Beijing 100048, China
2.
Department of Chemistry, Capital Normal University, Beijing 100048, China
3.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
4.
Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education(Nankai University), Tianjin 300071, China
5.
State Key Laboratory of Rare Earth Resource Utilization, Changchun 130022, China

Corresponding author: Qionghua JIN, jinqh204@163.com; jinqh@cnu.edu.cn
Received Date: 19 October 2023
Revised Date: 19 December 2023

Figures(9)

Two novel lanthanide bisphosphonate complexes containing Keggin polyoxometalates [Eu(L)₄]PW₁₂O₄₀· 2CH₃CN (1) and [Tb(L)₃(H₂O)]PW₁₂O₄₀ (2) (L=tetraethyl ethylenediphosphonate) were synthesized in a mixed solvent of acetonitrile and deionized water. The properties of the two complexes were characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis and terahertz time domain spectroscopy. The crystal structure and intermolecular weak force of the complexes were analyzed, and the luminescence and other properties of the complexes were studied. The single crystal X-ray diffraction indicates that the structure of complex 1 is a twisted tetragonal antiprism with Eu (Ⅲ) as the center and L as the ligands chelate. The structure of complex 2 is a twisted single-capped octahedral with Tb(Ⅲ) as the center and L and H₂O as the ligands. The luminescence spectra indicate that all emission peaks of complexes 1 and 2 are due to charge transfer within the metal. In addition, terahertz time-domain spectroscopy has helped in the study of complexes 1 and 2.
- lanthanide complexes,
- fluorescence spectroscopy,
- polyoxometalate,
- terahertz technology
1. [1]
  Hu Z Y, Haneklaus S, Sparovek G, Schnug E. Rare earth elements in soils[J]. Commun. Soil Sci. Plant Anal., 2006,37(9/10):1381-1420.
2. [2]
  Ramos S J, Dinali G S, Oliveira C, Martins G C, Moreira C G, Siqueira J O, Guilherme L R G. Rare earth elements in the soil environment[J]. Curr. Pollut. Rep., 2016,2(1):28-50. doi: 10.1007/s40726-016-0026-4
3. [3]
  Katkova M A, Bochkarev M N. New trends in design of electroluminescent rare earth metallo-complexes for OLEDs[J]. Dalton Trans., 2010,39(29):6599-6612. doi: 10.1039/c001152e
4. [4]
  Visseaux M, Bonnet F. Borohydride complexes of rare earths, and their applications in various organic transformations[J]. Coord. Chem. Rev., 2011,255(3/4):374-420.
5. [5]
  Yang Z Y, Yang R D, Li F S, Yu K B. Crystal structure and antitumor activity of some rare earth metal complexes with Schiff base[J]. Polyhedron, 2000,19(26/27):2599-2604.
6. [6]
  HUANG C H. Coordination chemistry of rare earth. Beijing: Science Press, 1997: 79-156
7. [7]
  LIU W S. Coordination chemistry. 2nd ed. Beijing: Chemical Industry Press, 2018: 24-28
8. [8]
  Li K, Chen J, Zou D, Deng Y F, Li D Q. Recovery of cerium(Ⅳ) in acidic nitrate solutions by solvent extraction with a novel extractant tris(2-ethylhexyl)phosphine oxide[J]. Hydrometallurgy, 2019,190105155. doi: 10.1016/j.hydromet.2019.105155
9. [9]
  Turanov A N, Matveeva A G, Kudryavtsev I Y, Pasechnik M P, Matveev S V, Godovikova M I, Baulina T V, Karandashev V K, Brel V K. Tripodal organophosphorus ligands as synergistic agents in the solvent extraction of lanthanides(Ⅲ). Structure of mixed complexes and effect of diluents[J]. Polyhedron, 2019,161:276-288. doi: 10.1016/j.poly.2019.01.036
10. [10]
  Lin C G, Hutin M, Busche C, Bell N L, Long D L, Cronin L. Elucidating the paramagnetic interactions of an inorganic-organic hybrid radical-functionalized Mn-Anderson cluster[J]. Dalton Trans., 2021,50(7):2350-2353. doi: 10.1039/D0DT04149A
11. [11]
  Sha J Q, Liang L Y, Sun J W, Tian A X, Yan P F, Li G M, Wang C. Significant surface modification of polyoxometalate by smart silver-tetrazolate units[J]. Cryst. Growth Des., 2012,12(2):894-901. doi: 10.1021/cg2013396
12. [12]
  Wang S S, Yang W B, Yang M X, Wu X Y, Wu W M, Wang S X, Lin L, Lu C Z. A bi-polyoxometallate-based host-guest metal-organic framework[J]. Chem. Comm., 2020,56(16):2503-2506. doi: 10.1039/C9CC09008H
13. [13]
  Zhu P P, Sun L J, Sheng N, Sha J Q, Liu G D, Yu L, Qiu H B, Li S X. Tuning the helical structures of Wells-Dawson polyoxometalate based hybrid compounds by using isomeric ligands[J]. Cryst. Growth Des., 2016,16(6):3215-3223. doi: 10.1021/acs.cgd.6b00119
14. [14]
  Luo X M, Li N F, Hu Z B, Cao J P, Cui C H, Lin Q F, Xu Y. Polyoxometalate-based well-defined rodlike structural multifunctional materials: synthesis, structure, and properties[J]. Inorg. Chem., 2019,58(4):2463-2470. doi: 10.1021/acs.inorgchem.8b03021
15. [15]
  Ma Y, Li Y G, Wang E B, Lu Y, Wang X L, Xu X X. Self-assembly of four new extended architectures based on reduced polyoxometalate clusters and cadmium complexes[J]. J. Solid State Chem., 2006,179(8):2367-2375. doi: 10.1016/j.jssc.2006.04.031
16. [16]
  Tian A, Han Z G, Peng J, Dong B X, Sha J Q, Li B. Two novel hybrid inorganic-organic compounds based on Wells-Dawson polyanion and transition metal (TM) complex with one-dimensional structure: Hydrothermal synthesis and characterization[J]. J. Mol. Struct., 2007,832(1/2/3):117-123.
17. [17]
  Tong R Z, Ren X Y, Li Z X, Liu B, Hu H M, Xue G L, Fu F, Wang J W. A novel extended architecture with 4⁶·6⁴ topology based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(Ⅰ) units[J]. J. Solid State Chem., 2010,183(9):2027-2031. doi: 10.1016/j.jssc.2010.07.004
18. [18]
  Wu H, Yang J, Liu Y Y, Ma J F. pH-controlled assembly of two unusual entangled motifs based on a tridentate ligand and octamolybdate clusters: 1D + 1D → 3D poly-pseudorotaxane and 2D → 2D → 3D polycatenation[J]. Cryst. Growth Des., 2012,12(5):2272-2276. doi: 10.1021/cg201555f
19. [19]
  Wang X L, Guo Y Q, Li Y G, Wang E B, Hu C W, Hu N H. Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: synthesis, structure, and fluorescent properties of[Ln₂(DNBA)₄(DMF)₈][Mo₆O₁₉] (DNBA=3, 5-dinitrobenzoate)[J]. Inorg. Chem., 2003,42(13):4135-4140. doi: 10.1021/ic0342447
20. [20]
  Zhang Z Y. Self-assembly of isopolyanion clusters and lanthanide- organic units into 2D layers: (NH₄)₂{[Ln₂(C₇H₄NO₄)₂(H₂O)₉][(H₂W₁₂O₄₀)]}·nH₂O (Ln=Gd, Tb, Ho)[J]. J. Clust. Sci., 2011,22(4):705-701. doi: 10.1007/s10876-011-0416-0
21. [21]
  Jin G Y, Zhang L, Hu F Z, Hu C, Lu Y L, Li Y Y, Han H L, Liu J M, Yang Y P, Jin Q H, Li X R. Photocatalysis, terahertz time domain spectroscopy and weak interactions of six polyoxometalate-based lanthanide phosphine oxide complexes[J]. CrystEngComm, 2022,24(29):5307-5316. doi: 10.1039/D2CE00779G
22. [22]
  Wang Z Q, Pan X, Lu Y L, Li Y Y, Yang Y P, Xin X L, Jin Q H. Crystal structures, terahertz spectra and dye adsorption performance of three lanthanide-bisphosphonate complexes containing Keggin polyoxometalates[J]. Chin. J. Struct. Chem., 2021,40(5):615-624.
23. [23]
  Wang Z Q, Sun L Z, Kuang X N, Lu Y L, Li Y Y, Yang Y P, Liu J M, Niu Y Y, Jin Q H. Intermolecular interactions, photocatalysis and THz-TDS interrelationships for lanthanide phosphine oxide complexes based on {PW₁₂}[J]. Environ. Res., 2022,203111873. doi: 10.1016/j.envres.2021.111873
24. [24]
  Hu C, Lu Y L, Li Y Z, Yang Y P, Liu M, Liu J M, Li Y Y, Jin Q H, Niu Y Y. Facile high yield, excellent catalytic performance of polyoxometalate-based lanthanide phosphine oxide complexes: Syntheses, structures, photocatalysis and THz spectra[J]. Environ. Res., 2022,206112267. doi: 10.1016/j.envres.2021.112267
25. [25]
  Hu C, Li Y Y, Qiu Q M, Han H L, Gu C Y, Yang Y P, Dai L X, Jin Q H. Efficient dye degradation and THz spectra of {PMo₁₂} based rare earth phosphine oxide complexes[J]. CrystEngComm, 2022,24(40):7166-7175. doi: 10.1039/D2CE00989G
26. [26]
  Xu S, Liu M, Yang Y P, Jiang Y H, Li Z F, Jin Q H, Wang X, Xue X N. Syntheses, structures, luminescence, NMR spectra and terahertz time-domain spectroscopy of nine lanthanide triflate complexes of tetrakis(O-isopropyl)methylenedisphosphonate with a L∶Ln ratio of 4∶1[J]. Polyhedron, 2015,87:293-301. doi: 10.1016/j.poly.2014.11.022
27. [27]
  Jepsen P U, Cooke D G, Koch M. Terahertz spectroscopy and imaging-modern techniques and applications[J]. Laser Photonics Rev., 2011,5(1):124-166. doi: 10.1002/lpor.201000011
28. [28]
  Krishnakumar V, Nagalakshmi R. Terahertz generation in 3-nitroaniline single crystals[J]. Cryst. Growth Des., 2008,8(11):3882-3884. doi: 10.1021/cg070548i
29. [29]
  Yang L M, Zhao G Z, Li W H, Liu Y F, Shi X X, Jia X F, Zhao K, Lu X Y, Xu Y Z, Xie D T, Wu J G, Chen J E. Low-frequency vibrational modes of DL-homocysteic acid and related compounds[J]. Spectrochim. Acta A Mol. Biomol. Spectrosc., 2009,73A(5):884-891.
30. [30]
  Sheldrick G M. Software for crystal structure analysis. Siemens Analytical X-ray Instruments Inc. Wisconsin: Madison, USA, 1997.
31. [31]
  Sheldrick G M. SHELXTL NT Version 5.1, program for solution and refinement of crystal structures. University of Gö;ttingen: Germany, 1997.
32. [32]
  Ma Y, Yang Y S, Jiang Y H, Li Y X, Liu M, Li Z F, Han H L, Yang Y P, Xin X L, Jin Q H. Lanthanide contraction and chelating effect on a new family of lanthanide complexes with tetrakis(O-isopropyl) methylenediphosphonate: synthesis, structures and terahertz time-domain spectroscopy[J]. RSC Adv., 2017,7(66):41651-41666. doi: 10.1039/C7RA07888A
33. [33]
  Haupt E T K, Kopf J, Petrova J, Arabadzhiev V, Momchilova S. Complexes of esters of ethylenediphosphonic acid with lanthanide nitrates-synthesis and structure[J]. Heteroat. Chem., 2006,17(1):36-46. doi: 10.1002/hc.20188
34. [34]
  Khder A E R S. Preparation, characterization and catalytic activity of tin oxide-supported 12-tungstophosphoric acid as a solid catalyst[J]. Appl. Catal. A-Gen., 2008,343(1/2):109-116.
35. [35]
  Matveeva A G, Vologzhanina A V, Goryunov E I, Aysin R R, Pasechnik M P, Matveev S V, Godovikov I A, Safiulina A M, Brel V K. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(Ⅲ) nitrates: Structural, spectroscopic and DFT characterization of the complexes[J]. Dalton Trans., 2016,45(12):5162-5179. doi: 10.1039/C5DT04963F
36. [36]
  Wei C, Sun B X, Zhao Z F, Cai Z L, Liu J J, Tan Y, Wei H B, Liu Z W, Bian Z Q, Huang C H. A family of highly emissive lanthanide complexes constructed with 6-(diphenylphosphoryl)picolinate[J]. Inorg. Chem., 2020,59(13):8800-8808. doi: 10.1021/acs.inorgchem.0c00444
37. [37]
  Lu Y L, Ma Y, Sun L Z, Kuang X N, Xin X L, Han H L, Liu M, Li Z F, Jin Q H. 1D lanthanide coordination polymers containing biphosphonate ligand: Synthesis, structures and luminescence properties[J]. Inorg. Chem. Commun., 2020,118108045. doi: 10.1016/j.inoche.2020.108045
38. [38]
  Wang C Y, Kang J, Zhang X Q, Zhao Y L, Chu H B. Crystal structures and luminescence properties of lanthanide complexes with 4-bromobenzoate and nitrogen heterocyclic ligands[J]. J. Lumin., 2019,215116638. doi: 10.1016/j.jlumin.2019.116638
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