Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst.

This study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe3+-doped titanium-based metal organic framework (MOF), xFeMIL125-NH2, as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy.

Local Coordination and Electronic Structure Ramifications of Guest-Dependent Spin Crossover in a Metal-Organic Framework: A Combined X-ray Absorption and Emission Spectroscopy Study.

The porous Hoffman-type 3D lattice Fe(pz)[Ni(CN)] exhibits thermally induced spin-crossover (SCO) behavior that is dependent on the solvent guest species occupying the pores. Here, in situ Fe K-edge X-ray absorption spectroscopy (XAS) and both non-resonant and resonant Kβ X-ray emission spectroscopy (XES) methods are used to probe this framework under two solvent environments that yield different extremes of spin crossover temperature: acetonitrile and toluene. While the acetonitrile pore environment engenders an SCO response around room temperature, toluene guests stabilize the high spin state and effectively suppress SCO behavior throughout the ambient temperature range.

High resolution x-ray emission spectrometer for multiple hard x-ray emission lines: Demonstration for Cu Kα and Kβ emissions.

We present a compact 3D printed x-ray emission spectrometer based on the von Hamos geometry that represents a significant upgrade to the existing von Hamos geometry-based miniature x-ray emission spectrometer (miniXES) [Mattern et al., Rev. Sci.

Heterometal incorporation in NH-MIL-125(Ti) and its participation in the photoinduced charge-separated excited state.

Optical and X-ray spectroscopy studies reveal the location and role of Fe3+ sites incorporated through direct synthesis in NH2-MIL-125(Ti). Fe K-edge XAS analysis confirms its metal-oxo cluster node coordination while time-resolved optical and X-ray transient absorption studies disclose its role as an electron trap site, promoting long-lived photo-induced charge separation in the framework. Notably, XTA measurements show sustained electron reduction of the Fe sites into the microsecond time range.

From IR to x-rays: gaining molecular level insights on metal-organic frameworks through spectroscopy.

This topical review focuses on the application of several types of spectroscopy methods to a class of solid state materials called metal organic frameworks (MOFs). MOFs are self-assembled, porous crystalline materials composed of metal cluster nodes linked through coordination bonds with organic or organometallic molecular constituents. Their unique host-guest properties make them attractive for many adsorption-based applications such as gas storage and separation, catalysis, sensing and others.