TY - JOUR

T1 - Photoluminescent lanthanide(iii) coordination polymers based on 2-{[(4-methylphenyl)amino]methylene}-5,5-dimethylcyclohexane-1,3-dione

AU - Smirnova, Ksenia S.

AU - Sanzhenakova, Elizaveta A.

AU - Eltsov, Ilia V.

AU - Pozdnyakov, Ivan P.

AU - Russkikh, Alena A.

AU - Dotsenko, Victor V.

AU - Lider, Elizaveta V.

N1 - The work was funded by Russian Science Foundation (the agreement no. 23-23-10028 of April 20, 2023) and the Government of the Novosibirsk region of the Russian Federation (agreement no. r-65 of April 3, 2023), project no. 23-23-10028. The authors thank A. P. Zubareva and N. N. Komardina for the elemental analysis, A. A. Shapovalova for IR spectroscopy, I. V. Yushina for recording diffuse reflectance spectra, A. S. Berezin for recording the kinetics of the complexes as well as phosphorescence spectrum, A. A. Ryadun for recording the quantum yields, M. O. Matveeva for the powder X-ray diffraction analysis, V. N. Yudin for providing the data collected in XRD Facility of NIIC SB RAS. The authors are grateful to the Ministry of Science and Higher Education of the Russian Federation (projects no. 121031700321-3 (NIIC) and FWGF-2021-0005(ICKC)).

PY - 2024/10/23

Y1 - 2024/10/23

N2 - Five novel lanthanide(iii) coordination polymers, namely, europium(iii), samarium(iii), terbium(iii), dysprosium(iii) and gadolinium(iii), with an enaminone derivative - 2-{[(4-methylphenyl)amino]methylene}-5,5-dimethylcyclohexane-1,3-dione (L), were obtained by two different synthesis methods. The composition and structure were investigated using IR spectroscopy, elemental analysis as well as powder and single-crystal X-ray diffraction (XRD) analysis. According to single-crystal XRD analysis data, the ligand exhibits bidentate bridging coordination mode, forming a polymer layered structure with the common formula [LnL2(NO3)3]n. All obtained compounds were isomorphous to each other. Upon investigating the photoluminescent properties, the quantum yield of the ligand was found to be 74%, but complex formation significantly decreased the quantum yield, such as for the europium complex, the quantum yield was only 7.6%. In the case of ligand, the kinetic curve was described by a biexponential function with luminescence lifetimes of 3.2 ns and 1.1 ns. For complexes, luminescence lifetime appeared in the millisecond region; it equalled 1.20 ms for the europium(iii) complex and 0.52 ms for the terbium(iii) complex. Triplet state energy was determined by both DFT calculations as well as registration of phosphorescence for the gadolinium(iii) complex. The highest color purity was found to be achieved at 95.58% in the case of the europium(iii) complex.

AB - Five novel lanthanide(iii) coordination polymers, namely, europium(iii), samarium(iii), terbium(iii), dysprosium(iii) and gadolinium(iii), with an enaminone derivative - 2-{[(4-methylphenyl)amino]methylene}-5,5-dimethylcyclohexane-1,3-dione (L), were obtained by two different synthesis methods. The composition and structure were investigated using IR spectroscopy, elemental analysis as well as powder and single-crystal X-ray diffraction (XRD) analysis. According to single-crystal XRD analysis data, the ligand exhibits bidentate bridging coordination mode, forming a polymer layered structure with the common formula [LnL2(NO3)3]n. All obtained compounds were isomorphous to each other. Upon investigating the photoluminescent properties, the quantum yield of the ligand was found to be 74%, but complex formation significantly decreased the quantum yield, such as for the europium complex, the quantum yield was only 7.6%. In the case of ligand, the kinetic curve was described by a biexponential function with luminescence lifetimes of 3.2 ns and 1.1 ns. For complexes, luminescence lifetime appeared in the millisecond region; it equalled 1.20 ms for the europium(iii) complex and 0.52 ms for the terbium(iii) complex. Triplet state energy was determined by both DFT calculations as well as registration of phosphorescence for the gadolinium(iii) complex. The highest color purity was found to be achieved at 95.58% in the case of the europium(iii) complex.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85207308686&origin=inward&txGid=d242145d26e17d06740068e9bd6489dd

UR - https://www.mendeley.com/catalogue/dd743b0f-a2af-3f92-a912-88d44af4642f/

U2 - 10.1039/d4nj03444a

DO - 10.1039/d4nj03444a

M3 - Article

VL - 48

SP - 18536

EP - 18545

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 43

ER -