Isomerization as a tool to design volatile heterometallic complexes with methoxy-substituted β-diketonates

Krisyuk, Vladislav V.; kyzy, Samara Urkasym; Rybalova, Т. V.; Байдина, И. А.; Korolkov, Ilya V.; Chizhov, D. L.; Bazhin, D. N.; Kudyakova, Yulia S.

doi:10.1080/00958972.2018.1479746

Cited by 19 publications

(11 citation statements)

References 23 publications

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“…Previously, it was shown that the monometallic complexes Cu(L 1 ) 2 , Cu(L 2 ) 2 , and Cu(L 3 ) 2 have the structure of coordination polymers and heterometallic complexes based on them can have both discrete and polymeric structures where the monometallic units are held together by bridging metal–oxygen bonds with the participation of methoxy groups [ 10 ]. For dimethoxy-substituted diketonate (L = L 1 , L 2 ), one of the adjacent methoxy groups in the terminal substituent remains free.…”

Section: Resultsmentioning

confidence: 99%

“…To overcome this problem, one can use ligands with donor atoms at the terminal substituents that are more sterically accessible to form bridging bonds with neighboring metal atoms, which should be coordination unsaturated. Our systematic screening of mono- and di-methoxy-substituted diketones, including the ones presented in Figure 1 (R-CO-CH-CO-C(OCH 3 ) x (CH 3 ) 3−x , x = 1, 2), allowed to prepare various heterometallic complexes by cocrystallization of monometallic complexes from organic solvents [ 10 , 11 , 12 ]. In the structure of such heterometallic complexes, the monometallic fragments are held together by bridging oxygen atoms, including those from methoxy groups.…”

Section: Introductionmentioning

confidence: 99%

“…In the structure of such heterometallic complexes, the monometallic fragments are held together by bridging oxygen atoms, including those from methoxy groups. For example in Cu/Pb and Pd/Pb heterocomplexes, it was shown that the structure and reactivity depend on the composition and structure of ligands in the initial monometallic complexes [ 10 , 11 ]. First-row transition metals with methoxy-substituted diketones form a series of coordination saturated binuclear complexes that are rather stable in solution and, therefore, are inert to the formation of heterometallic products [ 12 ].…”

Section: Introductionmentioning

confidence: 99%

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Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates

et al. 2022

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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.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates

et al. 2022

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“…On the other hand, the original structure of the complex is formed due to the lanthanide tris-β-diketonate fragment and initial lithium diketonate acting as the coligand. It is important that the additional functional group in the diketonate favors the formation of the heterobimetallic complexes with unique structures [16,17].…”

Section: Introductionmentioning

confidence: 99%

A Rare Example of Discrete Lanthanide–Lithium Tetrakis-β-Diketonates: Synthesis, Structures, and Luminescence Properties

et al. 2020

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The reactions of functionalized lithium CF 3 -β-diketonate (LiL) with europium(III) and terbium(III) chlorides in acetonitrile afford heterobimetallic complexes with the general formula [LiLnL 4 (H 2 O)](CH 3 CN) (Ln = Eu (IIIa) and Tb (IIIb)). It is found that Ln-Li tetrakis-β-diketonates can also be prepared by the crystallization from acetonitrile of the previously synthesized complexes [(LnL 3 )(LiL)(MeOH)] (I) and [(LnL 3 )(LiL)(H 2 O)] (II). For the first time, the single crystals of the compounds in a series of Ln-Li tetrakis-β-diketonates are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1973632 (IIIa) and 1973633 (IIIb)). The photoluminescence properties of the synthesized heterometallic complexes in the solid state are studied.

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“…Monoanionic, bidentate O,O '‐, N , N '‐, and N , O ‐chelating substituents such as β ‐diketonates I , β ‐diketiminates II , and β ‐ketoiminates III are widely used ligands in the coordination chemistry of main group and transition metals. Their steric and electronic properties can easily be tuned by variation of the R and R ' substituents and they were found to exhibit variable binding motifs, ranging from pure σ to a combination of σ and π donation .…”

Section: Introductionmentioning

confidence: 99%

Metal Complexes of Donor‐functionalized Fluorinatedβ‐Ketoiminates – Synthesis, Structure, and CVD Application

Kaiser

Ganesamoorthy

Wölper

et al. 2019

Zeitschrift anorg allge chemie

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Six alkali metal complexes of partly‐fluorinated, donor‐functionalized β‐ketoiminate ligands [L1Li (1), L1Na (2), L1K (3), L1Cs (4), L1 = OC(CF3)CHC(CH3)NCH2CH2OCH3; L2Li (5), L2Na (6), L2 = OC(CF3)CHC(CH3)NCH2CH2N(CH3)2] were prepared and structurally characterized. Reactions of L1Li with PtCl2 gave the homoleptic Pt complex L12Pt (7), which was characterized spectroscopically and by single‐crystal X‐ray diffraction and whose promising application as CVD precursor (chemical vapor deposition) is shown. Polycrystalline, pure Pt films were grown at 500 °C on SiO2@Si(100) substrates at 10–3 mbar and characterized by XRD, SEM, AFM, EDX and XPS.

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Isomerization as a tool to design volatile heterometallic complexes with methoxy-substituted β-diketonates

Cited by 19 publications

References 23 publications

Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates

Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-β-Diketonates

A Rare Example of Discrete Lanthanide–Lithium Tetrakis-β-Diketonates: Synthesis, Structures, and Luminescence Properties

Metal Complexes of Donor‐functionalized Fluorinatedβ‐Ketoiminates – Synthesis, Structure, and CVD Application

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