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 is improved compared to solid AZB. A population excited cis state up 30% has been obtained for AZB0.66@MIL-68(In). However, no observed AZB0.5@MIL-53(Al). Structural models from high-resolution...

Photorefraction is shown to arise generally with the generation of light-induced linkage isomers in compounds containing complexes [ML5NO]m±, where M a transition metal, L ligand, and m formal charge anion/cation (see figure inside cover). The photorefractive properties complex can be tuned by chemical variation L.

Nanocomposites have been processed following a wet-impregnation approach, by confined growth of nanoparticles the spin crossover complex [Fe(Htrz)2(trz)](BF4) within pre-formed transparent mesoporous silica monoliths well controlled porosity. The obtained materials were studied using numerous characterisation techniques to define interplay between porosity host matrix, structure and morphology in situ elaborated nanoparticles, properties composite. Transmission electron micrographs show...

In mononitrosyl complexes of transition metals two long-lived metastable states corresponding to linkage isomers the nitrosyl ligand can be induced by irradiation with appropriate wavelengths. Upon irradiation, N-bound (ground state, GS) turns into different conformations: isonitrosyl O bound for state 1 (MS1) and a side-on conformation 2 (MS2). Structural spectroscopic investigations on [RuCl(NO)py(4)](PF(6))(2)·1/2H(2)O (py = pyridine) reveal nearly 100% conversion from GS MS1. order...

1,3,3-Trimethylindolino-6'-nitrobenzopyrylospiran (SP-1) as an example of a photoswitchable spiropyran was loaded into the pores different prototypical metal-organic frameworks, namely MOF-5, MIL-68(In), and MIL-68(Ga), by vapor-phase process. The successful incorporation in MOF proven X-ray powder diffraction, amount embedded guest determined photoelectron spectroscopy elemental analysis. In contrast to sterically hindered crystalline state, SP-1 solid hosts shows photoswitching under...

Two light-induced metastable NO linkage isomers with oxygen-bound (SI) and side-on configuration (SII) of are generated in trans-[RuCl(py)4(NO)][PF6]2·½H2O. Irradiation by light the blue–green spectral range (450–530 nm) leads to population SI. A further irradiation near infrared (920–1100 transfers SI into SII at temperatures below 150 K. The heat release during thermal decay shows that separated from ground state (GS) potential barriers EA(SI) = 0.70(3) eV EA(SII) 0.38(3) eV, energetically...

Structure analysis of ground state (GS) and two light-induced (SI SII) metastable linkage NO isomers [Ru(py)4Cl(NO)](PF6)2.0.5H2O is presented. Illumination the crystal by a laser with lambda = 473 nm at T 80 K transfers around 92% ligands from Ru-N-O into isomeric configuration Ru-O-N (SI). A subsequent irradiation 980 generates about 48% side-on Ru<(N)(O) (SII). Heating to temperatures above 200 or light in red spectral range both reversibly back GS. Photodifference maps clearly show N-O...

We investigate the fundamental necessary conditions for optical generation of nitrosyl linkage isomers in ML5NO compounds (M = transition metal, L arbitrary ligand) on examples K3[Mn(CN)5NO]·2H2O and Na2[Fe(CN)5NO]·2H2O. show that NO side-on bonded type (SII, 90° rotation NO) isonitrosyl M–ON, where is O-bound to metal M (SI, 180° NO), can be generated if two are fullfilled. First excitation must lead a change bond between group central atom M, either by metal-to-ligand charge transfer d...

Abstract Fifteen new photochromic hybrid materials were synthesized by gas phase loading of fluorinated azobenzenes, namely ortho ‐tetrafluoroazobenzene ( tF ‐AZB), 4 H ,4 ′‐octafluoroazobenzene oF and perfluoroazobenzene pF into the pores well‐known metal‐organic frameworks MOF‐5, MIL‐53(Al), MIL‐53(Ga), MIL‐68(Ga), MIL‐68(In). Their composition was analysed elemental (CHNS) DSC/TGA. For ‐AZB 0.34 @MIL‐53(Al), a structural model based on high‐resolution synchrotron powder diffraction data...

We compare, from a crystallographic point of view, the data quality obtained using laboratory x-ray diffractometers equipped with Molybdenum micro-source different detector types: CCD, CMOS and XPAD hybrid pixel. First we give an overview working principle these types focus on their principal differences impact quality. Then, example organic crystal, comparison between systems concerning raw statistics, refinement agreement factors, deformation electron density maps, residual after...

Abstract Through photocrystallography at T = 80 K, light‐induced linkage isonitrosyl NO isomers (κO‐bound) are detected and refined in the complex fac ‐[RuNO(NO 2 ) Py OH] · H O (Py pyridine) after irradiation with light blue spectral range. The infrared Raman spectra reveal downshift of ν(NO), ν(Ru–NO), δ(Ru–N–O) vibrations by 120–150 cm –1 upon photoexcitation. Furthermore, spectrum show a significant ν as (NO s bands ca. 10 but without any isomerization ligands. downshifts ν(Ru–O–H)...

With the aim of enhancing biological activity ruthenium-nitrosyl complexes, new compounds with four equatorially bound indazole ligands, namely, trans-[RuCl(Hind)4(NO)]Cl2·H2O ([3]Cl2·H2O) and trans-[RuOH(Hind)4(NO)]Cl2·H2O ([4]Cl2·H2O), have been prepared from trans-[Ru(NO2)2(Hind)4] ([2]). When pH-dependent solution behavior [3]Cl2·H2O [4]Cl2·H2O was studied, two complexes deprotonated ligands were isolated, namely [RuCl(ind)2(Hind)2(NO)] ([5]) [RuOH(ind)2(Hind)2(NO)] ([6]). All...

Abstract Molecules, which reversibly transform between two structural configurations upon excitation with electromagnetic radiation, are attractive candidates for the design of smart materials e. g. memory devices. A possible approach development such is construction hybrid systems that contain these photochromic molecules as well a porous host matrix, enables their switching process in solid state. We herein present first light‐responsive consisting photoswitchable spirooxazine...

Transient light-induced absorption in LiNbO3 is observed the blue-green spectral range after pulsed illumination with 532 nm. Its buildup and decay Fe-doped satisfactorily described by a sum of two stretched exponential functions. For undoped LiNbO3, however, only one observed. These experimental results are explained formation both small Nb(Li)4+ electron polarons O- hole polarons. The mechanism discussed on basis proposed band scheme.

The existence of two light-induced long-lived metastable states SI, SII in irradiated trans-[Ru(NH3)4(H2O)NO]Cl3 x H2O and trans-[Ru(NH3)4(OH)NO]Cl2 is revealed by differential scanning calorimetry measurements calculations based on density functional theory. Irradiation with light the blue spectral range leads to population while can be obtained transferring SI into irradiation near infrared range. transfer described exponential functions thermal decays are evaluated according Arrhenius'...

The conditions for the photogeneration of NO linkage isomers at room temperature are studied. By pulsed laser irradiation in blue spectral range, long-lived Ru-ON isomer can be generated temperature, which is crucial potential applications, such as holography and data storage. using static time-resolved spectroscopy (UV/Vis IR), we give evidence that liftime Ru-(η2 -(NO)) a decisive parameter formation high owing to two-step isomerization mechanism Ru-NO→Ru-(η2 -(NO))→Ru-ON. Furthermore,...

Photoinduced linkage isomers (PLIs) of the nitro-ligand were generated and comprehensively characterized in a square planar unit [Pd(NH3)3NO2]+ complex salts [Pd(NH3)4][Pd(NH3)3NO2][MOx3]·yH2O (M = Cr (Cr), Rh (Rh), Co (Co), Ox oxalate). Structural (XRD) spectroscopic (IR, UV–vis) investigations at 10 150 K allowed determining structures several photoinduced isomers, endo-ONO (PLI1, 2) exo-ONO (PLI3, 4) by irradiation with 365 nm from initial NO2 (GS), along assignment infrared (IR) bands to...

We present a time-resolved absorption study on the light-induced generation of reversible linkage NO isomers in single crystals Na2[Fe(CN)5NO]·2H2O using laser pulses 160 fs width. Using pump wavelength λ = 500 nm singlet–singlet 1A1 → 1E excitation induces rotation by about 90° from linear Fe–N–O configuration to side-on Fe<NO. The formation isomer is monoexponential with characteristic time τ 300(20) and proceeds along diabatic potential surface without occupation further intermediate...

The ground state and the light-induced metastable states of ${\mathrm{Na}}_{2}[\mathrm{Fe}(\mathrm{CN}{)}_{5}\mathrm{NO}]\ensuremath{\cdot}2{\mathrm{H}}_{2}\mathrm{O}$ were investigated by polarized optical absorption spectroscopy on single crystals. An orbital level scheme is proposed for two SI SII. Based polarization analysis electronic transitions density calculations using functional theory (DFT), three tentatively assigned to calculated four that Isosbestic points at 562 375 nm in...

The temporal behavior of polarons generated by pulsed illumination $\mathrm{Li}\mathrm{Nb}{\mathrm{O}}_{3}$ crystals doped with Fe, $\mathrm{Fe}+\mathrm{Ti}$, and Cu is examined detecting the light-induced absorption ${\ensuremath{\alpha}}_{\mathrm{li}}$ in a pump-probe experiment. decay satisfactorily described stretched exponential function over range six decades. This fact attributed to dependence polaron lifetime on distance nearest deep traps or disorder...

One metastable linkage nitrosyl isomer can be generated in [Pt(NH3)4Cl(NO)]Cl2 by irradiation with light the red spectral range. The potential energy barrier for thermal relaxation of state to ground has an amount EA = (0.27 ± 0.03) eV. decay follows Arrhenius law and is independent temperature. At room temperature a lifetime τ 3.8 × 10−5 s after generation pulsed laser illumination. Below T 100 K about 30% NO isomers powder sample λ 658 nm. DFT calculations demonstrate rotation ligand from...

Nitro-nitrito photoisomerisation is investigated in solid samples and solutions of trans-[Ru(py)(4)(NO(2))(2)]. Using light wavelength 325 nm 50% the N-bound Ru-NO(2) ligands can be switched to O-bound Ru-ONO configuration (nitrito-N nitrito-O isomerisation) at temperatures below T = 250 K solids. The population isomeric configurations determined with infrared spectroscopy from decrease area nu(NO) stretching delta(NO) deformation modes. In a frozen methanol-ethanol solution nearly 100%...