Research output: Contribution to journal › Article › peer-review
Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates. / Krisyuk, Vladislav V.; Urkasym Kyzy, Samara; Rybalova, Tatyana V. et al.
In: Molecules, Vol. 27, No. 23, 8400, 12.2022.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates
AU - Krisyuk, Vladislav V.
AU - Urkasym Kyzy, Samara
AU - Rybalova, Tatyana V.
AU - Korolkov, Ilya V.
AU - Grebenkina, Mariya A.
AU - Lavrov, Alexander N.
N1 - Funding Information: This research was supported by the Ministry of Science and Higher Education of the Russian Federation, #121031700314-5 and #121031700313-8. Publisher Copyright: © 2022 by the authors.
PY - 2022/12
Y1 - 2022/12
N2 - The possibility of obtaining volatile polynuclear heterometallic complexes containing lanthanides and transition metals bound by methoxy-β-diketonates was studied. New compounds were prepared by cocrystallization of monometallic complexes from organic solvents. Ln(tmhd)3 were used as initial monometallic complexes (Ln = La, Pr, Sm, Gd, Tb, Dy, Lu; tmhd = 2,2,6,6-tetramethylheptane-3,5-dionate) in combination with TML2 in various ratios (TM = Cu, Co, Ni, Mn; L: L1 = 1,1,1-trifluoro-5,5-dimethoxypentane-2,4-dionate, L2 = 1,1,1-trifluoro-5,5-dimethoxy-hexane-2,4-dionate, L3 = 1,1,1-trifluoro-5-methoxy-5-methylhexane-2,4-dionate). Heterometallic complexes of the composition [(LnL2tmhd)2TM(tmhd)2] were isolated for light lanthanides Ln= La, Pr, Sm, Gd, and L= L1 or L2. By single crystal XRD, it has been established that heterometallic compounds containing La, Pr, Cu, Co, and Ni are isostructural linear coordination polymers of alternating mononuclear transition metal complexes and binuclear heteroleptic lanthanide complexes, connected by donor–acceptor interactions between oxygen atoms of the methoxy groups and transition metal atoms. A comparison of powder XRD patterns has shown that all heterometallic complexes obtained are isostructural. Havier lanthanides Ln = Tb, Dy, Lu did not form heterometallics. Instead, homometallic complexes Ln(L3)3 were identified for Ln = Dy, Lu as well as for Ln = La. The thermal properties of the complexes were investigated by TG-DTA and vacuum sublimation tests. The heterometallic complexes were found to be not volatile and decomposed under heating to produce inorganic composites of TM oxides and Ln fluorides. In contrast, Ln(L3)3 is volatile and may be sublimed in a vacuum. Results of magnetic measurements are discussed for several heterometallic and homometallic complexes.
AB - The possibility of obtaining volatile polynuclear heterometallic complexes containing lanthanides and transition metals bound by methoxy-β-diketonates was studied. New compounds were prepared by cocrystallization of monometallic complexes from organic solvents. Ln(tmhd)3 were used as initial monometallic complexes (Ln = La, Pr, Sm, Gd, Tb, Dy, Lu; tmhd = 2,2,6,6-tetramethylheptane-3,5-dionate) in combination with TML2 in various ratios (TM = Cu, Co, Ni, Mn; L: L1 = 1,1,1-trifluoro-5,5-dimethoxypentane-2,4-dionate, L2 = 1,1,1-trifluoro-5,5-dimethoxy-hexane-2,4-dionate, L3 = 1,1,1-trifluoro-5-methoxy-5-methylhexane-2,4-dionate). Heterometallic complexes of the composition [(LnL2tmhd)2TM(tmhd)2] were isolated for light lanthanides Ln= La, Pr, Sm, Gd, and L= L1 or L2. By single crystal XRD, it has been established that heterometallic compounds containing La, Pr, Cu, Co, and Ni are isostructural linear coordination polymers of alternating mononuclear transition metal complexes and binuclear heteroleptic lanthanide complexes, connected by donor–acceptor interactions between oxygen atoms of the methoxy groups and transition metal atoms. A comparison of powder XRD patterns has shown that all heterometallic complexes obtained are isostructural. Havier lanthanides Ln = Tb, Dy, Lu did not form heterometallics. Instead, homometallic complexes Ln(L3)3 were identified for Ln = Dy, Lu as well as for Ln = La. The thermal properties of the complexes were investigated by TG-DTA and vacuum sublimation tests. The heterometallic complexes were found to be not volatile and decomposed under heating to produce inorganic composites of TM oxides and Ln fluorides. In contrast, Ln(L3)3 is volatile and may be sublimed in a vacuum. Results of magnetic measurements are discussed for several heterometallic and homometallic complexes.
KW - beta-diketonates
KW - coordination polymer
KW - heterometallic complexes
KW - lanthanides
KW - ligand exchange
KW - molecular magnetism
KW - volatility
KW - Solvents
KW - Lanthanoid Series Elements/chemistry
KW - Transition Elements
KW - Magnetics
KW - Coordination Complexes/chemistry
UR - http://www.scopus.com/inward/record.url?scp=85143598983&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/7ed31988-ea10-3cff-8e2f-bfcca59380a9/
U2 - 10.3390/molecules27238400
DO - 10.3390/molecules27238400
M3 - Article
C2 - 36500492
AN - SCOPUS:85143598983
VL - 27
JO - Molecules
JF - Molecules
SN - 1420-3049
IS - 23
M1 - 8400
ER -
ID: 40813839