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A feasibility study on obtaining d-orbital populations from aspherical-atom refinements on three spin crossover compounds

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Abstract

Although compounds undergoing thermally induced spin crossover have been widely studied, their experimental d-orbital populations from single-crystal X-ray diffraction have rarely been reported. Three pairs of structures of iron/manganese coordination compounds were re-evaluated. Least-squares refinements relied on aspherical scattering factors obtained from molecular quantum-mechanical DFT single-point computations of the respective solid-state conformation, initiated by accurate starting structures from preliminary invariom refinements of the ligand environment. Further evaluation concerned d-orbital populations of metal ions from (a) single-point computations projected onto the Hansen-Coppens multipole model and from (b) experimental refinements of the metal atoms only. The latter were successful for good-quality data, independent of temperature, and provided only one spin state was exclusively present in the crystal. Crystals that underwent light-induced excited spin state trapping were not showing the expected d-orbital populations.

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Notes

  1. LIESST stands for light-induced exited spin state trapping.

  2. In the form of Fourier-Bessel transformed Hansen-Coppens multipole parameters.

  3. ADPs here stands for atomic displacement parameters.

  4. It should be emphasized that for data of conventional resolution (i.e., fulfilling resolution requirements for the Acta Crystallographica C and E journals), it is required to keep ADPs and possibly coordinates fixed from preliminary refinement with predicted scattering factors to suppress parameter correlation in the least-squares procedure.

  5. The original authors denote their data sets HS (LIESST), HS,LS (50%), and LS (reverse LIESST), respectively.

  6. The other ligands were generated to visualize the complete coordination environment.

  7. The corresponding author can provide positional parameters, experimental and calculated scattering factors, projected multipole parameters, and results of the quantum chemical calculations upon request.

  8. De-convolution is facilitated, since both sets of possibly correlated parameters of ADPs and multipoles are not refined simultaneously. A more thorough discussion is provided in [35].

  9. Four scattering factor databases currently exist: the ‘supramolecular-synthon based fragments approach’ SBFA [48], the ‘experimental library multipolar atom model’ ELMAM2 [49, 50] (both based on high-resolution experiments), the ‘generalized invariom database’ GID [33, 51], and the ‘University at Buffalo Databank’ UBDB2011 [52, 53] (the latter two based on theoretical DFT computations). All four rely on the established Hansen-Coppens multipole model [25] and can successfully be used to improve conventional XRD structures.

  10. The B3LYP functional and the D95 + +(3df,3pd) basis were used in the 2013 release of the database and for invariom modeling here. We can now also provide the M06/def2TZVP functional/basis set combination.

  11. Model compounds for this purpose were the same that have been used to derive the respective non-spherical hydrogen scattering factors [33].

  12. I.e. all scattering factors were now taken from the local ‘whole-molecule’ database, although for the ligand environment, it would not make a significant difference to keep the values from the invariom database.

  13. Note that the number of electrons of the metal atom are then also constrained due to the overall charge constraint.

  14. The artificial \(P\bar {1}\) unit cell with a = b = c = 30 Å [58] could therefore be used for FT with the program TONTO [59] throughout.

  15. The situation is more complicated for disordered structures.

  16. Bond distances showed that our result certainly was obtained for the supposed HS,HS data set and not the abovementioned third dataset of a HS,LS state.

  17. Here, the z-axis was defined by choosing the two nitrogen atoms of the phenanthroline ring as x- and y-axes. Orthogonalization then leads to the z-axis pointing to the thiocyanato ligand.

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Acknowledgments

Funding within DFG project DI 921/6-1 is gratefully acknowledged. The authors thank Prof. G. Morgan for sharing their multi-temperature X-ray data for compound 2 and the referees for helpful suggestions and corrections as well as Dr. F.P.A. Fabbiani for improvements of the manuscript.

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  1. Institut für Anorganische Chemie und Strukturchemie, Material- und Strukturforschung, Heinrich-Heine Universität Düsseldorf, Gebäude: 26.42, Universitätsstraße 1, 40225, Düsseldorf, Germany

    Birger Dittrich

  2. Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146, Hamburg, Germany

    Birger Dittrich, Erik Ruf & Tobias Meller

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Dittrich, B., Ruf, E. & Meller, T. A feasibility study on obtaining d-orbital populations from aspherical-atom refinements on three spin crossover compounds. Struct Chem 28, 1333–1342 (2017). https://doi.org/10.1007/s11224-017-1012-1

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