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. 2019 Nov 6;27:104758. doi: 10.1016/j.dib.2019.104758

Density functional theory calculated data of different electronic states and bond stretch isomers of tris(trifluoroacetylacetonato)-manganese(III)

Jeanet Conradie 1
PMCID: PMC6864354  PMID: 31763410

Abstract

In this data article, using density functional theory calculations, it is shown that in the gas phase, free from crystal packing effects, different elongation and compression Jahn-Teller geometries of fac and mer tris(trifluoroacetylacetonato)-manganese(III) are possible. A careful construction of input geometries made it possible to obtain the density functional theory calculated optimized geometries of different elongation and compression Jahn-Teller geometries of fac and mer tris(trifluoroacetylacetonato)-manganese(III). The mer CF3–CF3 elongation isomer has the lowest energy (Fig. 1), while in the solid state a mer CH3–CH3 compression tris(trifluoroacetylacetonato)-manganese(III) isomer is experimentally characterized [1]. The rare experimental example of a compression tris(β-diketonato)-manganese(III) structure is ascribed to intermolecular F⋯F and F⋯H interactions between the tris(trifluoroacetylacetonato)-manganese(III) molecules in the solid crystalline state, contributing to the distortion of the coordination polyhedron of tris(trifluoroacetylacetonato)-manganese(III) from the expected elongation Jahn-Teller geometry, to the observed higher energy electronic state with compression Jahn-Teller distortion.

Keywords: Jahn–Teller, DFT, Elongation, Manganese(III)trifluoroacetylacetonato, High-spin

Specifications Table

Subject Chemistry
Specific subject area Computational and structural chemistry.
Type of data Table
Image
Figure
How data were acquired Electronic structure calculations, using the Amsterdam Density Functional (ADF) 2018 programme.
Data format Raw
Analyzed
Parameters for data collection Suitable xyz coordinates for the input geometries were constructed using CHEMCRAFT. The input coordinates were used in the input file of the ADF program, an example input file is provided in the supplementary information.
Description of data collection Data were collected from ADF output files
Data source location Department of Chemistry, University of the Free State, Nelson Mandela Street, Bloemfontein, South Africa
Data accessibility With the article
Related research article Roxanne Gostynski, Petrus H.van Rooyen, Jeanet Conradie
X-ray diffraction and QTAIM calculations of the non-covalent intermolecular fluorine-fluorine interactions in tris(trifluoroacetylacetonato)-manganese(III).
Journal of Molecular Structure 1201 (2020) 127119, https://doi.org/10.1016/j.molstruc.2019.127119
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Value of the Data
  • •

    DFT calculated optimized structural data (coordinates) of different fac and mer tris(trifluoroacetylacetonato)-manganese(III) isomers are provided for structural and computational chemistry researchers.

  • •

    Data provide geometrical and electronic structure of elongation and compression Jahn-Teller geometries of fac tris(trifluoroacetylacetonato)-manganese(III).

  • •

    Data provide geometrical and electronic structure of elongation Jahn-Teller geometries of three different bond stretch isomers of mer tris(trifluoroacetylacetonato)-manganese(III).

  • •

    This data can be used to understand the different electron occupation of elongation and compression Jahn-Teller geometries of high spin tris(trifluoroacetylacetonato)-manganese(III).

  • •

    This data can be used to visualize the molecular orbitals involved in elongation or compression Jahn-Teller geometries of high spin tris(trifluoroacetylacetonato)-manganese(III).

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1. Data

In Fig. 1 the splitting of the molecular energy levels containing d-electrons for high spin, S = 2, d4 (t2g3eg1) octahedral transition metal complexes such as tris(trifluoroacetylacetonato)-manganese(III) are illustrated [2,3]. The splitting leads to either elongation (z-out) Jahn-Teller distortion with the highest molecular orbital (HOMO) of dz2 character, or to compression (z-in) Jahn-Teller distortion with a HOMO of dx2−y2 character. For high spin d4 mer tris(trifluoroacetylacetonato)-manganese(III) the elongation (or compression) can occur along three different O–Mn–O bonds, leading to three different bond stretch isomers for mer tris(trifluoroacetylacetonato)-manganese(III). Although only one mer tris(trifluoroacetylacetonato)-manganese(III) isomer is experimentally characterized by solid state crystal data [1], density functional theory calculations can determine the structure of the different electronic state and bond stretch isomers for both fac and mer tris(trifluoroacetylacetonato)-manganese(III). Fig. 2 shows the electron density isosurface, as well as the highest occupied molecular orbital (HOMO) and lowest unoccupied orbital (LUMO) of both the elongation and compression Jahn-Teller structures of B3LYP-D3/TZP optimized fac tris(trifluoroacetylacetonato)-manganese(III). The elongation structure is 0.05 eV lower in energy than the compression fac tris(trifluoroacetylacetonato)-manganese(III) structure. The HOMO of the elongation Jahn-Teller structure is of dz2 character and the LUMO of dx2−y2 character, in agreement with the theoretical splitting of the molecular orbital energy levels as shown in Fig. 1(a). The HOMO of the compression Jahn-Teller structure is of dx2−y2 character and the LUMO of dz2 character, in agreement with the theoretical splitting of the molecular orbital energy levels as shown in Fig. 1(b). Fig. 3 shows the electron density isosurface, as well as the HOMO and LUMO of the different elongation Jahn-Teller structures of B3LYP-D3/TZP optimized mer tris(trifluoroacetylacetonato)-manganese(III). Table 1 provides the relative energies of the different elongation isomers of tris(trifluoroacetylacetonato)-manganese(III) as obtained by a selection of DFT functionals. The energies of the different isomers are very near to each other, implying that all isomers may exist, though all functionals predict the mer CF3–CF3 isomer to be the most stable.

Fig. 1.

Fig. 1

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Illustration of the theoretical splitting of the energy levels containing d-electrons of high spin S = 2, d4 (t2g3eg1) octahedral transition metal complexes from octahedral, due a Jahn-Teller stabilization energy, leading to either (a) a tetragonal elongation (z-out) or (b) a tetragonal compression (z-in) geometry. (c) The z-axis can be aligned along different O–Mn–O bonds for the fac (one unique possibility) and mer (three different possibilities) isomers of tris(trifluoroacetylacetonato)-manganese(III).

Fig. 2.

Fig. 2

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Visualization of the (a) Electron density isosurface (contour 0.08 e/Å3), (b) HOMO and (c) LUMO (contour 0.03 e/Å3) of the compression (top) and elongation (bottom) of B3LYP-D3/TZP optimized fac tris(trifluoroacetylacetonato)-manganese(III). Colour code use for molecule: C (grey), O (red), H (white), F (green) and Mn (turquoise).

Fig. 3.

Fig. 3

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Visualization of the (a) Electron density isosurface (contour 0.08 e/Å3), (b) HOMO and (c) LUMO (contour 0.03 e/Å3) of the different elongation isomers of B3LYP-D3/TZP optimized mer tris(trifluoroacetylacetonato)-manganese(III). Colour code use for molecule: C (grey), O (red), H (white), F (green) and Mn (turquoise).

Table 1.

Relative energies of the different elongation isomers of fac and mer tris(trifluoroacetylacetonato)-manganese(III) optimized with the indicated functionals.

Isomer ΔE (eV)
B3LYP-D3 BP86-D3 M06-L PW91 OLYPa
fac 0.024 0.046 0.117 0.036 0.044
mer CF3–CF3 0.000 0.000 0.000 0.000 0.000
mer CF3–CH3 0.017 0.029 0.026 0.029 0.030
mer CH3–CH3 0.011 0.023 0.025 0.054 0.064
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a

From Ref. [4].

2. Experimental design, materials, and methods

Density functional theory (DFT) calculations were performed in the gas phase on the neutral molecule, using the Amsterdam Density Functional (ADF) 2018 programme [5]. Results obtained by five different functionals in combination with the TZP (Triple ζ polarized) basis set are reported, namely: OLYP (Handy-Cohen and Lee-Yang-Parr) [[6], [7], [8], [9]], B3LYP-D3 [7,10], PW91 [11], BP86-D3 [12,13] and M06-L [14,15]. Input coordinates were constructed using ChemCraft [16]. Chemcraft and ADF gui was used to visualize the ADF output and t21 files respectively. The optimized coordinates, as well as an example input file, are provided in the supplementary information.

The DFT optimization process are very sensitive to the input geometry, since difference in the energies of the different isomers are small. In some cases the “NumericalQuality good” and “ExactDensity” options in the input file led to the required isomer. An example input file, as well as the optimized coordinates as obtained by the different functionals, and a set of output files, are provided in the supplementary information.

Acknowledgments

This work has received support from the South African National Research Foundation (Grant numbers 113327 and 96111) and the Central Research Fund of the University of the Free State, Bloemfontein, South Africa. The High-Performance Computing facility of the UFS , the CHPC of South Africa and the Norwegian Supercomputing Program (UNINETT Sigma2, Grant No. NN9684K) are acknowledged for computer time.

Footnotes

Appendix A

Supplementary data to this article can be found online at https://doi.org/10.1016/j.dib.2019.104758.

Conflict of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Appendix A. Supplementary data

The following are the Supplementary data to this article:

Multimedia component 1
mmc1.zip (800.4KB, zip)
Multimedia component 2

Input and output files and optimized coordinates of DFT calculations.

mmc2.doc (136KB, doc)

References

  • 1.Freitag R., van Rooyen P.H., Conradie J. X-ray diffraction and QTAIM calculations of the non-covalent intermolecular fluorine-fluorine interactions in tris(trifluoroacetylacetonato)-manganese(III) J. Mol. Struct. 2020;1201:127119. [Google Scholar]
  • 2.Freitag R., Conradie J. Understanding the Jahn-Teller Effect in octahedral transition metal complexes – a Molecular Orbital view of the Mn(β-diketonato)3 complex. J. Chem. Educ. 2012;90(12):1692–1696. [Google Scholar]
  • 3.Halcrow M.A. Jahn-Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials. Chem. Soc. Rev. 2013;42(4):1784–1795. doi: 10.1039/c2cs35253b. [DOI] [PubMed] [Google Scholar]
  • 4.Gostynski R., Conradie J., Erasmus E. Significance of electron-density of molecular fragments on the properties of manganese(III) β-diketonato complexes: an XPS and DFT study. RSC Adv. 2017;7:27718–27728. [Google Scholar]
  • 5.te Velde G., Bickelhaupt F.M., Baerends E.J., Fonseca Guerra C., van Gisbergen S.J.A., Snijders J.G., Ziegler T. Chemistry with ADF. J. Comput. Chem. 2001;22:931–967. [Google Scholar]
  • 6.Handy N.C., Cohen A.J. Left-right correlation energy. Mol. Phys. 2001;99:403–412. [Google Scholar]
  • 7.Lee C., Yang W., Parr R.G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B Condens. Matter. 1988;37:785–789. doi: 10.1103/physrevb.37.785. [DOI] [PubMed] [Google Scholar]
  • 8.Johnson B.G., Gill P.M.W., Pople J.A. The performance of a family of density functional methods. J. Chem. Phys. 1993;98:5612–5626. [Google Scholar]
  • 9.Russo T.V., Martin R.L., Hay P.J. Density Functional calculations on first-row transition metals. J. Chem. Phys. 1994;101:7729–7737. [Google Scholar]
  • 10.Becke A.D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993;98:5648–5652. [Google Scholar]
  • 11.Perdew J.P., Chevary J.A., Vosko S.H., Jackson K.A., Pederson M.R., Singh D.J., Fiolhais C. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. 1992;B46:6671–6687. doi: 10.1103/physrevb.46.6671. Erratum: J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A. Jackson, M.R. Perderson, D.J. Singh, C. Fiolhais, Phys. Rev. B48 (1993) 4978. [DOI] [PubMed] [Google Scholar]
  • 12.Becke A.D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A. 1988;38:3098–3100. doi: 10.1103/physreva.38.3098. [DOI] [PubMed] [Google Scholar]
  • 13.Perdew J.P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Physical Reviews B. 1986;33:8822–8824. doi: 10.1103/physrevb.33.8822. Erratum: J.P. Perdew, Physical Reviews B 34 (1986) 7406. [DOI] [PubMed] [Google Scholar]
  • 14.Zhao Y., Truhlar D.G. A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J. Chem. Phys. 2006;125:194101–194118. doi: 10.1063/1.2370993. [DOI] [PubMed] [Google Scholar]
  • 15.Zhao Y., Truhlar D.G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008;120:215–241. [Google Scholar]
  • 16.ChemCraft Version 1.8 Built 428. 2015. https://www.chemcraftprog.com/

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Multimedia component 1
mmc1.zip (800.4KB, zip)
Multimedia component 2

Input and output files and optimized coordinates of DFT calculations.

mmc2.doc (136KB, doc)

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