Анотація
The study presents a comparative analysis of the spectral-luminescent properties of synthesized β-diketonate coordination complexes of ytterbium with the following ligands: 2,7-dimethyl-oct-1-en-3,5-dione, 2,6-dimethyl-hept-1-en-3,5-dione, 2-methyl-5-phenylpent-1-en-3,5-dione, 2-methyl-5-biphenylpent-1-en-3,5-dione. In addition, research was conducted on polymeric compounds based on these complexes and their phenanthroline mixed-ligand derivatives.
Using a range of physicochemical analysis methods, it was established that the structure of the elementary unit during polymerization, as well as the coordination sphere of the complexes during the formation of mixed-ligand compounds, does not undergo significant changes compared to the initial β-diketonate molecules. Thermal analysis revealed a significant increase in the decomposition onset temperature of mixed-ligand and metallopolymeric compounds compared to their monomeric counterparts. Luminescence spectroscopy demonstrated that the studied samples exhibit luminescence in the infrared (IR) range.
A comparative analysis of the integral luminescence intensities of ytterbium complexes identified key factors influencing the emission characteristics. Primarily, the synthesis of mixed-ligand complexes with phenanthroline mitigates the negative effects of one of the most well-known quenching factors: OH-oscillators of water molecules, which complement the coordination sphere of monomeric ytterbium complexes. Furthermore, the synthesis of polymeric compounds based on β-diketonate complexes positively affects the luminescence, potentially due to a reduction in concentration quenching, as in polymers, the emitting centers are uniformly distributed along the macromolecular chain. Besides directly enhancing luminescent properties, this approach aims to address the practical application of the synthesized compounds since polymers are significantly easier to process and can form film materials.
Based on the conducted research, the following luminescence intensity dependencies were established: dmod>dmhpd>mbphpd>mphpd, as well as monomer-polymer-MLC-MLC polymer. As seen from the presented data, the best emission characteristics are exhibited by ytterbium mixed-ligand mono- and polycomplexes with β-diketones containing alkyl substituents.
Посилання
Nehra K., Dalal A., Hooda A., Bhagwan S., Saini R. K., Mari B., Kumar S., Singh D. Lanthanides β-diketonate complexes as energy-efficient emissive materials: A review. Journal of Molecular Structure. 2022. 1249: 131531.
https://doi.org/10.1016/j.molstruc.2021.131531.
Ning Y., Zhu M., Zhang J.-L. Near-infrared (NIR) lanthanide molecular probes for bioimaging and biosensing. Coord. Chem. Rev. 2019. 399.
https://doi.org/10.1016/j.ccr.2019.213028.
Cao J., Zhang R., Chen L., Wang D., Wang W., Tan E., Meng X., Xiu H., Wang L., Yang X., Yang Z., Yang Q., Zhao L. Design strategies and applications of responsive metal-based luminescence probes in the bioanalysis. TrAC Trends in Analytical Chemistry. 2023. 168: 117338.
https://doi.org/10.1016/j.trac.2023.117338.
Cheng P. Chapter 8 - Lanthanides in biosensing. In: Cheng P., editor. Lanthanides. Elsevier. 2023. 409–540.
https://doi.org/10.1016/B978-0-12-822250-8.00008-4.
Cheng P. Chapter 9 - Lanthanides in bioimaging. In: Cheng P., editor. Lanthanides. Elsevier. 2023. 541–647.
https://doi.org/10.1016/B978-0-12-822250-8.00009-6.
Dalal A., Nehra K., Hooda A., Singh D., Kumar P., Kumar S., Malik R. S., Rathi B. Luminous lanthanide diketonates: Review on synthesis and optoelectronic characterizations. Inorganica Chimica Acta. 2023. 550:121406.
https://doi.org/10.1016/j.ica.2023.121406.
Sun Z., Sun L. Chapter 337 – Rare-earth upconversion luminescence and its applications: from molecular to nano and micro scales. In: Bünzli J.-C. G., Kauzlarich S. M., editors. Handbook on the Physics and Chemistry of Rare Earths. 2024. 65. 1–33.
https://doi.org/10.1016/bs.hpcre.2024.03.001.
Balmus D. Novel stable ytterbium acetylacetonate–quinaldinate complexes as single-molecule magnets and surprisingly efficient luminophores.Dalton Transactions. 2023.
https://doi.org/10.1039/D3DT03253A
Fan, W.; Wang, H.; Huang, X.; Shi, T.; Du, J.; Xu, H. B. Energy transfer process, luminescence optimizing and various applications of lanthanide complexes. Chem. Synth. 2024, 4, 12.
http://dx.doi.org/10.20517/cs.2023.35
Berezhnytska O., Horbenko A., Savchenko I., Rohovtsov O., Rusakova N., Trunova O. Investigation of coordination compounds of Gadolinium (III) with β-diketones. Chem. Chem. Technol. 2023. 17(4): 748–757.
https://doi.org/10.23939/chcht17.04.748
Su L., Liu X., Niua Q., Li G. Photoresponsive lanthanide luminescent materials J. Mater. Chem. C. 2024. 12: 10759–10774.
https://doi.org/10.1039/D4TC01353K
Ahmed Z., Mahiya K., Iftikhar K. Synthesis, crystal structure, NMR and near infra-red luminescence studies of nine-coordinate Nd and Yb complexes based on fluorinated β diketone and a tridentate antenna chromophore, 2, 4, 6-Tris-(2-pyridyl)-s-triazine. Inorganica Chimica Acta. 2022. 541: 121086.
https://doi.org/10.1016/j.ica.2022.121086.
Bhat, S. A., Hasan, N., Zargar, R. A., Wankar, S., Rawat, J. Evidencingthe NIR luminescence and longer lifetime from ytterbium complex constructed from perfluorinated β-diketone and heteroatom based ancillary ligand. Journal of Molecular Structure. 2024. 1299: 137016.
https://doi.org/10.1016/j.molstruc.2023.137016
Hasegawa M., Ohmagari H., Tanaka H., Machid K. Luminescence of lanthanide complexes: From fundamental to prospective approaches related to water- and molecular-stimuli. Journal of Photochemistry and Photobiology C: Photochemistry Reviews. 2022. 50: (100484).
doi.org/10.1016/j.jphotochemrev.2022.100484
Brito-Santos G., Gil-Hernández B., Martín I. R., Guerrero-Lemus R., Sanchiz J. Visible and NIR emitting Yb (III) and Er (III) complexes sensitized by β-diketonates and phenanthroline derivatives. RSC advances. 2020. 10(46): 27815–27823.
https://doi.org/10.1039/D0RA05539E
Santos H. P., Gomes E. S., dos Santos M. V., D’Oliveira K. A., Cuin A., Martins J. S., Quirino W. G., Marques L. F. Synthesis, structures and spectroscopy of three new lanthanide β-diketonate complexes with 4,4′-dimethyl-2,2′-bipyridine. Near-infrared electroluminescence of ytterbium(III) complex in OLED. Inorganica Chimica Acta. 2019. 484: 60–68.
https://doi.org/10.1016/j.ica.2018.09.030.
Ning Y., Tang J., Liu Y., Jing J., Sun Y., Zhang J. Highly luminescent, biocompatible ytterbium(III) complexes as near-infrared fluorophores for living cell imaging. Chem. Sci. 2018. 9: 3742–3753.
https://doi.org/10.1039/C8SC00259B
Staszak K., Wieszczycka K., Marturano V., Tylkowski B. Lanthanides complexes – Chiral sensing of biomolecules. Coordination Chemistry Reviews. 2019. 397: 76–90.
https://doi.org/10.1016/j.ccr.2019.06.017.
Dasari S., Singh S., Kumar P., Sivakumar S., Patra A. K. (). Near-infrared excited cooperative up conversion in luminescent Ytterbium (ΙΙΙ) bioprobes as light-responsive the ranosticagents. European Journal of Medicinal Chemistry. 2019. 163: 546–559.
https://doi.org/10.1016/j.ejmech.2018.12.010,
Fan S., Yao X., Li J., Li W., Li G. Near-infrared luminescent materials: From β-diketonate ytterbium complexes to β-diketonate-ytterbium-complex@PMMA thin film. Journal of Luminescence. 2018. 203. 473–480.
https://doi.org/10.1016/j.jlumin.2018.07.003.
Yang D., Li H., Li H. Recent advances in the luminescent polymers containing lanthanide complexes. Coord. Chem. Rev. 2024. 514: 215875. https://doi.org/10.1016/j.ccr.2024.215875
Zhang Z., Yu C., Liu L., Li H., He Y., Lü X., ... & Jones R.A. Efficient near-infrared (NIR) luminescent PMMA-supported hybrid materials doped with tris-β-diketonate Ln3+ complex (Ln= Nd or Yb). Journal of Photochemistry and Photobiology A: Chemistry. 2016. 314: 104–113.
https://doi.org/10.1016/j.jphotochem.2015.08.022
Ivakha N., Berezhnytska O., Rohovtsov O., Rusakova N., Trunova O. Mono- andmixed- ligand complexes of Yb(III) with new β-diketones. Ukrainian Chemistry Journal. 2021. 87(2): 65–76.
https://doi.org/10.33609/2708-129X.87.02. 2021.65-76
Ivakha N., Berezhnytska O., Rohovtsov O., Trunova O., Smola S. Investigation of new polymer complexes based on Yb (III) β-diketonates. Ukrainian Chemistry Journal. 2022. 88(5): 3–14.
https://doi.org/10.33609/2708-129X.88.05. 2022.3-14
Berezhnytska O., Savchenko I., Ivakha N., Trunova O., Rusakova N., Smola S., Rogovtsov O. Synthesis, characterization, and luminescent properties of polymer complexes of Nd (III) with β-dicarbonyl ligands. Nanoscale Research Letters. 2017. 12: 1–8.
https://doi.org/10.1186/s11671-017-2074-0
Savchenko I., Berezhnytska O., Fedorov Ya., Smola S., Trunova O. Luminescent properties of new polymer metal complexes based β-diketones and REE. Molecular Crystals and Liquid Crystals, 2018. 673(1): 48–60.
https://doi.org/10.1080/15421406.2019.1578493
Ivakha N.B., Berezhnytska O.S., Rohovtsov O.O., Trunova O.K. Complexes of Nd(III) and Er(III) with novel unsutaratedβ-diketones. Ukr. Chem. J. 2019. 85 (6): 87–96. [in Ukrainian]
https://doi.org/10.33609/0041-6045.85.6. 2019.87-96
Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 2009, Sixth Edition, Part B, Wiley, Hoboken, New Jersey.
Larkin P. Infrared and Raman spectroscopy: principles and spectral interpretation. 2017 Elsevier. Amsterdam.
Kofod N., Nawrocki P., Platas-Iglesias C., &Sørensen T. J. Electronic structure of ytterbium (III) solvates – a combined spectroscopic and theoretical study. Inorganic chemistry. 2021. 60(10): 7453–7464.
https://doi.org/10.1021/acs.inorgchem.1c00743
Yatsimirskii K.B., Davidenko N.K. Absorption spectra and structure of lanthanide coordination compounds in solution. Coordination Chemistry Reviews. 1979. 27(3): 223–273. https://doi.org/10.1016/S0010-8545(00)82068-8
daSilva P.S.P., Martín-Ramos P., Silva M.R., Lavín V., Chamorro-Posada P., Martín-Gil J. X-ray analysis, molecular modeling and NIR-luminescence of erbium (III) 2, 4-octanedionate complexes with N,N-donors. Polyhedron. 2014. 81: 485–492.
https://doi.org/10.1016/j.poly.2014.07.006
Martín-Ramos P., da Silva P. S. P., Lavín V., Martín I. R., Lahoz F., Chamorro-Posada P., ... & Martin-Gil J. Structure and NIR-luminescence of ytterbium (III) beta-diketonate complexes with 5-nitro-1, 10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact. Dalton Transactions. 2013. 42(37): 13516–13526.