Dominik Schaniel

Metal–Organic Frameworks as Hosts for Photochromic Guest Molecules

Several metal-organic framework compounds (MOF-5, MIL-68(Ga), MIL-68(In), MIL-53(Al)) were loaded with azobenzene (AZB), as confirmed by XRPD measurements and elemental analysis. By IR spectroscopy, it was shown that the light-induced trans/cis isomerization of AZB in these hybrid host-guest compounds is improved compared to that of solid AZB. A population of the excited cis state up to 30% has been obtained for AZB0.66@MIL-68(In). However, no light-induced trans/cis isomerization was observed for AZB0.5@MIL-53(Al). Structural models obtained from high-resolution synchrotron powder diffraction data show that AZB molecules are densely packed within the channels of MIL-53(Al) so that no trans/cis isomerization can occur. A different situation was observed for AZB in the larger channels of MIL-68(Ga). Thus, this investigation shows the influence of the host material on the switching behavior of the embedded AZB molecules.

(Ru(py)4Cl(NO))(PF6)2 0.5H2O: a model system for structural determination and ab initio calculations of photo-induced linkage NO isomers

Structure analysis of ground state (GS) and two light-induced (SI and SII) metastable linkage NO isomers of [Ru(py)4Cl(NO)](PF6)2.0.5H2O is presented. Illumination of the crystal by a laser with lambda = 473 nm at T = 80 K transfers around 92% of the NO ligands from Ru-N-O into the isomeric configuration Ru-O-N (SI). A subsequent irradiation with lambda = 980 nm generates about 48% of the side-on configuration Ru<(N)(O) (SII). Heating to temperatures above 200 K or irradiation with light in the red spectral range transfers both metastable isomers reversibly back to the GS. Photodifference maps clearly show the N-O configurations for both isomers and they could be used to find a proper starting model for subsequent refinements. Both metastable isomers have slightly but significantly different cell parameters with respect to GS. The main structural changes besides the Ru-O-N and RU<(N)(O) linkage are shortenings of the trans Ru-Cl bonds and the equatorial Ru-N bonds. The experimental results are compared with solid-state calculations based on density functional theory (DFT), which reproduce the observed structures with high accuracy concerning bond lengths and angles. The problem of how the different occupancies of SI and GS could affect refinement results was solved by a simulation procedure using the DFT data as starting values.

Ultrafast reversible ligand isomerisation in Na2[Fe(CN)5NO]·2H2O single crystals

We present a time-resolved absorption study on the light-induced generation of reversible linkage NO isomers in single crystals of Na(2)[Fe(CN)(5)NO] x 2 H(2)O using laser pulses of 160 fs width. Using the pump wavelength lambda = 500 nm the singlet-singlet (1)A(1)-->(1)E excitation induces the NO rotation by about 90 degrees from the linear Fe-N-O configuration to a side-on configuration [structure: see text]. The formation of the isomer is monoexponential with a characteristic time of tau = 300(20) fs and proceeds along a diabatic potential surface without occupation of further intermediate states. The side-on structure has a lifetime of 270(30) ns at T = 23 degrees C.

Photogeneration of nitrosyl linkage isomers in octahedrally coordinated platinum complexes in the red spectral range.

Octahedrally coordinated platinum nitrosyl complexes [Pt(NH(3))(4)(NO(3))(NO)](NO(3))(2) (1) and [Pt(NH(3))(4)(SO(4))(NO)](HSO(4))(CH(3)CN) (2) undergo linkage isomerization at temperatures below 130 K when excited with red light. Irradiation in the spectral range of 570-800 nm results in an inversion of the NO ligand from a Pt-NO to a Pt-ON configuration. The metastable state Pt-ON can be reverted back to the ground state (GS) Pt-NO by irradiation with blue-green or infrared light or by heating above 130 K. The characteristic shift of the nu(NO) stretching vibration from 1744 to 1815 cm(-1) in 1 and from 1714 to 1814 cm(-1) in 2 allowed the unambiguous identification of the respective nitrosyl isomers. Up to 26% of the complexes of 1 and 20% of 2 may be photochemically excited toward the metastable state (MS). Using X-ray crystallography and DFT calculations, it is shown that the Pt-NO in these {MNO}(8) complexes exhibits a bent arrangement with a Pt-N-O angle in the range of 117-120 degrees. As a consequence and in contrast to the known {MNO}(6) complexes only one metastable linkage isomer Pt-ON with a correspondingly bent Pt-O-N arrangement is formed, as evidenced by spectroscopy and DFT calculations. The calculated partial density of states shows that the charge transfer transition Pt(5d) --> pi(star)(NO) is responsible for the formation of the metastable state.

Reducing the positional modulation of NbO6-octahedra in SrxBa1–xNb2O6 by increasing the barium content: A single crystal neutron diffraction study at ambient temperature for x = 0.61 and x = 0.34

Abstract We report on the influence of the barium content on the modulation amplitude in SrxBa1–xNb2O6 compounds by comparing Sr0.61Ba0.39Nb2O6 (SBN61) and Sr0.34Ba0.66Nb2O6 (SBN34). Our single crystal neutron diffraction results demonstrate that the amplitude of the positional modulation of the NbO6 octahedra is reduced with increasing barium content, indicating that the origin of the modulation is the partial occupation of the pentagonal channels by Sr and Ba atoms. By increasing the Sr content the bigger Ba atoms are replaced by the smaller Sr atoms, which leads to a larger deformation of the surrounding lattice and hence to a larger modulation amplitude. The more homogeneous the filling of these channels with one atomic type (Ba) the lower the modulation amplitude. Our results also show that the structure can be described with a two-dimensional incommensurate harmonic modulation. No second order modulation has been observed, both by single crystal diffraction measurements and q-scans. The positional modulation of the Nb atoms is much smaller than that of the oxygen atoms, such that the modulation can be seen as a rotational modulation of almost rigid NbO6-octahedra.

Pulse recording of thermal and linkage isomer gratings in nitrosyl compounds

Two different kinds of short-lived phase gratings are written with identically and orthogonally polarized waves using nanosecond laser pulses in single crystals of the nitrosyl compounds Na2[Fe(CN)5NO]⋅2H2O, (CN3H6)2[Fe(CN)5NO], and Ba[Fe(CN)5NO]⋅3H2O. With identically polarized recording beams thermal gratings are written by the thermo-optic effect, which results from the spatially modulated thermo-optic coefficient ∂n/∂T. The lifetime τdif of such gratings depends quadratically on the spatial grating frequency K with the thermal diffusion coefficient Ddif as the material parameter: τdif=Ddif−1K−2. Upon recording with mutually orthogonally polarized beams no intensity modulation occurs, but the resulting modulation of the polarization leads to the generation of light-induced linkage NO-isomers with varying efficiency according to the local state of the light polarization. This rotation of the NO ligand by nearly 90° results in a modulation of the polarizability and with this of the refractive index of the crystal.

Structural properties of Sr{sub 0.61}Ba{sub 0.39}Nb{sub 2}O{sub 6} in the temperature range 10-500 K investigated by high-resolution neutron powder diffraction and specific heat measurements

We report high-resolution neutron powder diffraction on Sr{sub 0.61}Ba{sub 0.39}Nb{sub 2}O{sub 6} in the temperature range 15-500 K. The results indicate that the low-temperature anomalies (T{<=}100 K) observed in the dielectric dispersion are due to small changes in the incommensurate modulation of the NbO{sub 6} octahedra, as no structural phase transition of the average structure was observed. This interpretation is supported by specific heat measurements, which show no latent heat, but a glass-like behavior at low temperatures. Furthermore, we find that the structural changes connected with the ferroelectric phase transition at T{sub c}{approx_equal}350 K start already at 200 K, explaining the anisotropic thermal expansion in the temperature range 200-300 K observed in a recent x-ray diffraction study.

Properties of metastable linkage NO isomers in Na2[Fe(CN)5NO]·2H2O incorporated in mesopores of silica xerogels

We study the properties of photoinduced metal-nitrosyl linkage isomers in sodium nitroprusside (SNP) as a function of particle size. By embedding the molecular complex at various concentrations into mesopores of silica xerogels the size of the particles can be adjusted. The ground state is characterized by X-ray diffraction, absorption and infrared spectroscopy. The physical properties of the photoswitched molecules were analysed by steady-state low-temperature absorption, infrared spectroscopy and by nanosecond transient absorption spectroscopy. The electronic structure as well as the activation energies of the metastable linkage isomers are independent of the particle size down to single isolated molecules, indicating that the SNP complexes are quasi-free inside the pores of the gel.

Multiple light-induced NO linkage isomers in the dinitrosyl complex [RuCl(NO)2(PPh3)2]BF4 unravelled by photocrystallographic and IR analysis

Photocrystallographic and IR analysis reveal light-induced reversible metastable NO linkage isomers in the dinitrosyl compound [RuCl(NO)2(PPh3)2]BF4.

Neutron photocrystallography : simulation and experiment

Abstract The investigation of light-induced structural changes by diffractive methods has improved significantly in the last two decades. We present here the case of neutron photocrystallography for which we have built a special experimental setup at the single crystal neutron diffractometer TriCS at the Swiss Spallation Neutron Source SINQ. We illustrate the progress of the method on the example of the structural determination of photoinduced nitrosyl linkage-isomers in Na2[Fe(CN)5NO] · 2 H2O. The in-situ determination of the population of the light-induced linkage isomers by optical transmission measurements enhances the reliability of such structural investigations considerably. Additionally we present a new simulation tool within the program package JANA2006 which allows to plan a photocrystallographic experiment thoroughly since the required q-range, the minimally needed population of the photoinduced species, as well as the necessary counting statistics for a successful single crystal diffraction experiment can be evaluated in advance.