ABSTRACT
The incorporation of photochromic dyes into porous metal-organic frameworks (MOFs) is an attractive way to transfer the photochromic properties of the dye to a solid crystalline material. In this work, the well-known P-type chromophore 1,2-bis[2-methylbenzo[b]thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-1-cyclopentene (DTE) is embedded in three different MOFs, namely MOF-5, MIL-68(In), and MIL-68(Ga). The successful filling of the MOF pores with the DTE guest was proven by X-ray powder diffraction, while the amount of the embedded guest molecules was investigated by X-ray photoelectron spectroscopy (XPS), liquid-state NMR and thermal analysis (DSC/TGA). The measurements reveal an unexpectedly low filling of the MOF pores with the DTE guest (e.g. in MOF-5 only every fifth MOF pore is filled with a guest molecule) as well as an inhomogeneous loading throughout the material. Reflection spectra clearly show the transitions of the colourless open-ring and the coloured closed-ring forms of the DTE guest upon UV (λ = 365 nm), blue (λ = 405 nm) and green (λ = 535 nm) light exposure, where the latter is usually suppressed in crystalline DTE. Remarkably, no fatigue after ten switching cycles was observed and a high thermal stability of the coloured closed-ring form (at 50 °C for 1 h) was achieved.
ABSTRACT
Cs2Cd(C2H)2(C2) was synthesized by heating known Cs2Cd(C2H)4 either in a dry argon atmosphere at 200 °C or under ammonothermal conditions (130 °C, â¼ 100 bar). The crystal structure of the resulting dark orange-brown microcrystalline material was solved and refined from synchrotron powder diffraction data (Cmcm, Z = 4). Cs2Cd(C2H)2(C2) is composed of Cd2+ cations tetrahedrally coordinated end-on by four acetylide groups. Two of them are terminating C2H- groups, whereas the other two positions are occupied by bridging C22- anions. Thus, a polymeric ∞1[Cd(C2H)2(C2)2/22-] chain-like anion results and these chains are separated by Cs+ cations. So obviously Cs2Cd(C2H)2(C2) is formed from Cs2Cd(C2H)4 by a condensation reaction of two of its four C2H- groups under the release of one acetylene (C2H2) molecule. This reaction mechanism is supported by DSC/TGA measurements, and the crystal structure of Cs2Cd(C2H)2(C2) is further supported by IR spectroscopic investigations.
ABSTRACT
Fifteen new photochromic hybrid materials were synthesized by gas phase loading of fluorinated azobenzenes, namely ortho-tetrafluoroazobenzene (tF-AZB), 4H,4H'-octafluoroazobenzene (oF-AZB), and perfluoroazobenzene (pF-AZB), into the pores of the well-known metal-organic frameworks MOF-5, MIL-53(Al), MIL-53(Ga), MIL-68(Ga), and MIL-68(In). Their composition was analysed by elemental (CHNS) and DSC/TGA. For pF-AZB0.34 @MIL-53(Al), a structural model based on high-resolution synchrotron powder diffraction data was developed and the host-guest and guest-guest interactions were elucidated from this model. These interactions of O-Hâ â â F and πâ â â π type were confirmed by significant shifts of the O-H frequencies in loaded and unloaded MOFs of the MIL-53 and MIL-68 series. Most remarkably, all of the synthesized F-AZB@MOF systems can be switched with visible light, and some of them show almost quantitative (>95 %) photo-isomerization between its E and Z forms with no significant fatigue after repeated switching cycles.
ABSTRACT
By reaction of alkali metal acetylides, AI C2 H (AI =K, Rb, Cs), with elemental selenium in liquid ammonia highly crystalline powders of AI SeC2 H were obtained. The structure analysis based on the resulting synchrotron powder diffraction data revealed that all compounds crystallize in an orthorhombic unit cell (Cmc21 , Z=4) exhibiting the elusive - SeC2 H anion, which is unprecedented in a crystalline compound up to now. Elemental analysis and IR spectroscopic data confirm this finding. Upon heating, AI SeC2 H compounds release acetylene based on DSC/TGA experiments resulting in powders with the proposed composition AI 2 Se2 (C2 ). The resulting powders were indexed with small cubic unit cells, but a reasonable structural model could not be developed up to now. Upon exposure of AI SeC2 H compounds to water elemental selenium is formed again.