Jahn-Teller distortion in tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]manganese(III) isomers: An X-ray and computational study

Properties of Manganese(III) Ferrocenyl-β-Diketonato Complexes Revealed by Charge Transfer and Multiplet Splitting in the Mn 2p and Fe 2p X-Ray Photoelectron Envelopes

“…Our XPS measurements, however, shows experimentally they are different. To place this experimental result in perspective, it is useful to note that DFT calculations on a similar set of tris(β-diketonato)manganese(III) complexes revealed there is an energy difference between mer and fac HOMO energies [44]. Since EHOMO has been proven to be related to binding energies obtained from XPS [30,45,46], it follows that there must also be a difference between the binding energies of the fac and mer isomers.…”

Significance of the electron-density of molecular fragments on the properties of manganese(iii) β-diketonato complexes: an XPS and DFT study

“…show that for 1-9, the elongation Jahn-Teller distortion geometry is generally more stable than the compression Jahn-Teller distortion geometry, see Table 1. 26,30 Both elongation 31 as well as compression Jahn-Teller distortion 32,33 has experimentally been observed in crystal structures obtained for [Mn(b-diketonato) 3 ] complexes. However, compression Jahn-Teller distortion as observed for [Mn(acac) 3 ], 33 has actually been attributed to an unusual consequence of unknown crystal packing effects, 34 stating that typically the tetragonal elongation is the "natural" Jahn-Teller effect of [Mn(acac) 3 ], in agreement with the DFT calculations obtained in this study (Hacac ¼ acetylacetone).…”

“…The OLYP functional proved to be a good choice for correctly calculating the ground state of high spin 3d metalcomplexes. 26,[85][86][87][88][89] To further support the reliability of the computational method used in this work, the S ¼ 1 (two unpaired electrons) and S ¼ 2 (four unpaired electrons) spin states of [Mn(acac) 3 ] as representative example of [Mn(bdiketonato) 3 ] complexes, were optimized using a selection of functionals, see Table 3. These results indicate that the OLYP, B3LYP, CAM-B3LYP (B3LYP with long-range correction), M06-D3 (M06 with the Grimme empirical dispersion correction) and M065X functionals correctly predicted the experimental high state of S ¼ 2 of [Mn(acac) 3 ], in agreement with experimental EPR studies.…”

“…2(d). 26,30 The OLYP/ TZP energies for these four (including the one fac) different elongation [Mn III (b-diketonato) 3 ] isomers of unsymmetrical complexes 3, 5-8, are given in Table 1. The DFT calculations show that for these unsymmetrical complexes 3, 5-8, (i) the most stable isomer is a mer isomer, (ii) the fac isomer is generally slightly less stable than the different mer isomers, and (iii) the energy differences between the different bond stretch isomers of [Mn(b-diketonato) 3 ] complexes are small.…”

“…By adding the XPS data of [Mn III (b-diketonato) 3 ] complexes, where the b-diketonato ligand does not contain an electron donating ferrocenyl group, we hereby enlarge the range of binding energies of the Mn 2p photoelectron lines by nearly 100%, to a range of 1.07 eV. Thus, in continuation of our interest in the geometrical 25,26 and electronic structure 27 of [Mn(b-diketonato) 3 ] complexes containing b-diketonato ligands with different electrondonating and -withdrawing properties, we hereby present a combined study of theoretical quantum chemistry calculations (using density functional theory, DFT) and experimental measurements (using XPS) on the series of nine non-ferrocene-containing [Mn(bdiketonato) 3 ] complexes shown in Fig. 1 (with b-diketonato ¼ dipivaloylmethanato (1), acetylacetonato (2), benzoylacetonato characterised by two short bonds along the z-direction, as well as four long bonds in the xy-plane, and a d-electron occupation of d 1…”