TY - JOUR

T1 - Polymeric REE coordination compounds based on novel enaminone derivative

AU - Smirnova, K. S.

AU - Ivanova, E. A.

AU - Eltsov, I. V.

AU - Pozdnyakov, I. P.

AU - Russkikh, A. A.

AU - Dotsenko, V. V.

AU - Lider, E. V.

N1 - Funding Information: This work was supported by the Russian Science Foundation (Project №20-73-10207) and the Ministry of Science and Higher Education of the Russian Federation, №121031700321-3 (Nikolaev Institute of Inorganic Chemistry SB RAS). Triplet state measurements of gadolinium complex were supported by a grant from the Russian Science Foundation (Project №19-73-20196) and performed in the “Center for Optical and Laser materials research” (St. Petersburg State University, St. Petersburg, Russian Federation). The authors thank Anna P. Zubareva and Natalia N. Komardina for the elemental analysis, Anastasia O. Matveeva for the X-ray phase analysis data, Alexandra A. Shapovalova for IR-spectroscopy data, Pavel E. Plyusnin for thermogravimetric analysis, Taisiya S. Sukhikh, Vladislav Yu. Komarov and Denis G. Samsonenko for providing the data collected in XRD Facility of NIIC SB RAS, Alexey A. Ryadun for phosphorescence measurements. Publisher Copyright: © 2022 Elsevier Ltd

PY - 2022/11/15

Y1 - 2022/11/15

N2 - A novel enaminone derivative, 2-{[(3-methoxyphenyl)amino]methylene}-5,5-dimethylcyclohexane-1,3-dione (HL) and its lanthanide(III) complexes [Ln(HL)2(NO3)3]n have been prepared. The composition and structure of products have been investigated using IR-spectroscopy, elemental and X-ray diffraction analysis (powder and single-crystal). HOMO/LUMO, as well as triplet state energy has been established by means of DFT calculations. According to the single-crystal X-ray diffraction analysis, the enaminone ligand exhibits bidentate-bridging coordination resulting in polymeric net. All obtained complexes are isomorphous to each other. Photoluminescence of free ligand in polycrystalline state is very low; the quantum yield is only 0.33%, most probably due enhancement of internal conversion in the singlet excited state by the presence of methoxy substituent. Energy transfer from the ligand to lanthanide ions is observed only for europium(III) and, in less extent, samarium(III) complexes.

AB - A novel enaminone derivative, 2-{[(3-methoxyphenyl)amino]methylene}-5,5-dimethylcyclohexane-1,3-dione (HL) and its lanthanide(III) complexes [Ln(HL)2(NO3)3]n have been prepared. The composition and structure of products have been investigated using IR-spectroscopy, elemental and X-ray diffraction analysis (powder and single-crystal). HOMO/LUMO, as well as triplet state energy has been established by means of DFT calculations. According to the single-crystal X-ray diffraction analysis, the enaminone ligand exhibits bidentate-bridging coordination resulting in polymeric net. All obtained complexes are isomorphous to each other. Photoluminescence of free ligand in polycrystalline state is very low; the quantum yield is only 0.33%, most probably due enhancement of internal conversion in the singlet excited state by the presence of methoxy substituent. Energy transfer from the ligand to lanthanide ions is observed only for europium(III) and, in less extent, samarium(III) complexes.

KW - DFT-calculations

KW - Enaminone

KW - Lanthanide(III) complexes

KW - Photoluminescence

KW - Polymeric structure

UR - http://www.scopus.com/inward/record.url?scp=85137617298&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2022.116122

DO - 10.1016/j.poly.2022.116122

M3 - Article

AN - SCOPUS:85137617298

VL - 227

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

M1 - 116122

ER -