Effect of fluorosubstitution in the ligand on structure, spectral and thermal characteristics of trimethylplatinum β-diketonate complexes

• Published in: Journal of fluorine chemistry Vol. 249; p. 109843
• Main Authors: Dorovskikh, Svetlana I., Klyamer, Darya D., Mirzaeva, Irina V, Pyrayzev, Dmitry A., Pishur, Denis P., Krasnov, Pavel O., Basova, Tamara V., Morozova, Natalia B.
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01-09-2021; Elsevier BV
• Subjects: Band theory; Crystal structure; Crystallography; Crystals; Cyclin-dependent kinase inhibitor p21; Density functional theory; DFT calculations; Hirshfeld surface analysis; Infrared spectroscopy; IR spectroscopy; Mathematical analysis; Molecular structure; Monoclinic lattice; Packaging; Surface analysis (chemical); TG-DTA; Thermal properties; Thermodynamic properties; trimethylplatinum(IV) β-diketonates; Vibrational spectra; Hirshfeld surface analysis; TG-DTA; trimethylplatinum(IV) β-diketonates; IR spectroscopy; DFT calculations; Crystal structure
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2021.109843

•The crystal packing of Me3Pt(L)Py molecules is sensitive to F content in the ligand.•The π...π interactions appeared in the structures of fluorinated complexes.•Molecule deformation in the crystals of complexes may affect their volatility.•Fluorinated complexes exhibit high volatility and stability up to melting.
This work is aimed at studying the structures, IR spectra and thermal properties of the series of trimethylplatinum complexes (Me3Pt(L)Py) with various combinations of β-diketonate (CβCOCγHCOCβ’) substituents: (1) Cβ,Cβ’=Me, acac - pentan-2,4-dionato; (2) Cβ=Me, Cβ’=CF3, tfac - 1,1,1-trifluoro-2,4-pentanedionato; (3) Cβ,Cβ’=CF3, hfac - 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato; (4) Cβ=tBu, Cβ’=CF3, ptac - 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione;
(5) Cβ=Me, Cβ’=C2F5, 5Fac - 1,1,1,2,2-pentofluoro-3,5-hexandionato; (6) Cβ=Me, Cβ’=C3F7, 7Fac - 1,1,1,2,2,3,3-heptafluoro-4,6-heptandionato; Py - pyridine. The following crystallographic parameters, namely monoclinic P21/n, Z = 4, a = 11.8927(4) Å, b = 8.8446(4) Å, c = 16.9802(6) Å, β = 107.2490(10)°, V = 1705.75(11) Å3 and monoclinic P21/c, Z = 8, a = 9.7297(14) Å, b = 35.709(5) Å, c = 10.6785(11) Å, β = 91.035(2)°,V = 3709.5(8) Å3 have been determined for the crystals of 5 and 6, respectively. Hirshfeld surface analysis was used as a tool for visualization of intermolecular contacts and packaging features in the structures of Me3Pt(L)Py molecules depending on the combination of substituents in L. The effect of combination of β-diketonate substituents on the molecular structure and vibrational spectra of Me3Pt(L)Py derivatives was also studied. The density functional theory (DFT) calculations were used for the assignment of bands in their IR spectra. The thermal behavior of Me3Pt(L)Py complexes in the condensed phase were studied using TG, DSC methods. The complex 3 was tested as a precursor in MOCVD experiments.
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