Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements: experimental methodology and results
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Sébastien Pillet
Abstract
The electron density distribution of a light-induced molecular excited state, i.e. the high spin metastable state of [Fe(phen)2(NCS)2], was determined from steady-state photocrystallographic measurements. We defined the experimental conditions under which the accuracy of the measured diffraction data is compatible with an electron density analysis. These include: (i) a large structural and electronic contrast between high spin (HS) and low spin (LS) states, (ii) an efficient photoconversion under light irradiation and (iii) slow relaxation of the HS metastable state. Multipolar modeling of the electron density yielded a deformation density and 3d-orbital populations for Fe(II) characteristic of a high spin (t2g4eg2) electron configuration and support the assumption of significant σ-donation and π-backbonding of the Fe—N interactions. The electron density distribution in the intermolecular regions confirms anisotropic intermolecular interactions with possibly a layer topology parallel to the orthorhombic (ab) plane, related to the system cooperativity.
© Oldenbourg Wissenschaftsverlag
Articles in the same Issue
- Preface: Photocrystallography
- Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements: experimental methodology and results
- Light-induced phase separation (LIPS) into like-spin phases observed by Laue neutron diffraction on a single crystal of [Fe(ptz)6](BF4)2
- Neutron photocrystallography: simulation and experiment
- Static and time-resolved photocrystallographic studies in supramolecular solids
- State of the art and opportunities in probing photoinduced phase transitions in molecular materials by conventional and picosecond X-ray diffraction
- Real-time studies of reversible lattice dynamics by femtosecond X-ray diffraction
- Towards pump-probe resonant X-ray diffraction at femtosecond undulator sources
- Exploiting EXAFS and XANES for time-resolved molecular structures in liquids
- Home-based time-resolved photo small angle X-ray diffraction and its applications
- DFT study of crystalline nitrosyl compounds
- Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them
- DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes
- Excited state isomerization in photochromic ruthenium complexes
- Applications of photocrystallography: a future perspective
Articles in the same Issue
- Preface: Photocrystallography
- Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements: experimental methodology and results
- Light-induced phase separation (LIPS) into like-spin phases observed by Laue neutron diffraction on a single crystal of [Fe(ptz)6](BF4)2
- Neutron photocrystallography: simulation and experiment
- Static and time-resolved photocrystallographic studies in supramolecular solids
- State of the art and opportunities in probing photoinduced phase transitions in molecular materials by conventional and picosecond X-ray diffraction
- Real-time studies of reversible lattice dynamics by femtosecond X-ray diffraction
- Towards pump-probe resonant X-ray diffraction at femtosecond undulator sources
- Exploiting EXAFS and XANES for time-resolved molecular structures in liquids
- Home-based time-resolved photo small angle X-ray diffraction and its applications
- DFT study of crystalline nitrosyl compounds
- Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them
- DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes
- Excited state isomerization in photochromic ruthenium complexes
- Applications of photocrystallography: a future perspective
