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

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.

Effect of density functional approximations on the calculated Jahn–Teller distortion in bis(terpyridine)manganese(III) and related compounds

“…(iii) M06 functional [ 26 ] with basis set 6-311G(d,p). The M06 [ 25 ] functional, in agreement with the OLYP [ 24 ], BP86 [ 25 ], and B3LYP [ 25 ] functionals, proved to give the same Jahn–Teller ground state for high-spin d 4 Mn(III) [ 25 ].…”

“…(ii) B3LYP functional [ 19 , 23 ] with basis set 6-311G(d,p). The B3LYP functional, in agreement with the OLYP [ 24 ], BP86 [ 25 ], and M06-L [ 25 ] functionals, proved to give the same Jahn–Teller ground state for high-spin d 4 Mn(III) [ 25 ]. The B3LYP functional also proved to correctly calculate both the and ground states of the Jahn–Teller active high-spin d 4 Cr(II) and low spin Cu(II) octahedral complexes [ 3 ].…”

Effect of metal ions in the electron-transfer mechanism on the photovoltaic performance of SALPHEN-based DSSC: experimental and theoretical studies

“…The natural transition orbitals (NTOs) were derived for [Fe(SALPHEN)Cl(H 2 O)], [Co(SALPHEN)(H 2 O)], and [Cu(SALPHEN)] to determine the particle-hole position in the excited-state using B3LYP/DGDZVP. 55,56 The charge difference density was also calculated by three-dimensional (3D) visualization of the electron density isosurface (contour 0.05 e Å À3 ). The HOMO and LUMO were derived for the complexes using B3LYP/DGDZVP to understand the influence of their structure on the performance of the DSSC.…”