Metal atom dynamics in organometallics: Cyano ferrocenes

Electronic Properties of Mono‐Substituted Tetraferrocenyl Porphyrins in Solution and on a Gold Surface: Assessment of the Influencing Factors for Photoelectrochemical Applications

“…[28] Molecular orbital contributions were compiled from single point calculations using the QMForge program. [29] In all single-point calculations and geometry optimizations, Becke's exchange functional and the Pedrew 86 correlation functional (BP86) [30] was used because as it was shown before, GGA-based exchange-correlation functionals provide a good electronic structure description for ferrocene-containing molecules, [31] including ferrocenylporphyrins. [17] Use of hybrid B3LYP [32] or PBE1PBE [33] exchange-correlation functionals lead to heavy infusion of porphyrin-centered p-electron density into the HOMO region, which was not supported by the experimental data.…”

Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: Long range orbital coupling via porphyrin core

“…This, however, has not yet been confirmed from the point of theoretical investigation because of the lack of theoretical calculations in this regard. On the other hand, density functional theory (DFT) and time dependant density functional theory (TD-DFT) methods have proved suitable for the calculation of the energy-minimized structures, electronic distribution, molecular orbitals, electron transfer, and electronic absorption spectra of a series of porphyrin and phthalocyanine derivatives [17][18][19][20][21][22][23] as well as ferrocene derivatives [24][25][26][27][28][29]. As a consequence, towards understanding the long range electronic coupling between ferrocenyl groups connected via porphyrin framework, theoretical studies over multi-component compounds composed of porphyrin and ferrocenyl units appear interesting.…”

Metal atom dynamics in organometallics: Vibrational amplitude determination for bis phosphino ferrocenes including a waxy system

“…(b) Mössbauer spectroscopy (ME): These compounds were examined by transmission spectroscopy as previously described [4,5]. Spectrometer calibration was effected by the use of a 20 mg m cm À2 a Fe absorber at room temperature, and all isomer shifts are referenced to the centroid of such calibration spectra.…”

“…Compound 3, which is a waxy material at room temperature, was transferred to the sample holder as received. Temperature monitoring and control, as well as data reduction, have been described previously [4,5].…”

“…In the past decade it has also become evident that temperature-dependent Mössbauer effect (ME) spectroscopy can serve to elucidate the bonding and dynamical behavior of the iron atom in such complexes and thus lead to a better understanding of the role of the metal center in the chemistry of these precursors to catalytically active solids [4]. In addition, it has been shown that such spectroscopy can be used to evaluate the vibrational behavior of the iron center and such data can be compared to the thermal factors (U i,j ) extracted from single crystal X-ray diffraction studies [5]. One of the advantages of the ME technique is that it can lead to an evaluation of the root-mean-square-amplitude-of-vibration (rmsav) over a wide temperature range even in non-crystalline materials.…”