UV-Visible-Near IR Spectrophotometer for the Study of Reactive Chemical Species and Small-Molecule Reactivity in Metal-Organic Frameworks

We seek funding for an Ultraviolet-Visible-Near Infrared (UV-Vis-NIR) spectrometer setup to enable studies of reactive chemical species isolated within metal-organic frameworks (MOFs). This setup will enhance the quality of research currently funded through ARO, which aims to (1) isolate reactive species within MOFs, such as terminal metal oxo and nitrido functionalities, and (2) carry out and study stoichiometric and catalytic activation of small molecules. The UV-Vis-NIR setup will enhance and advance this work by enabling the facile collection of spectra under a wide range of experimental conditions, which will facilitate detailed examinations of both geometric and electronic structures and reactivity patterns of the targeted materials. The UV-Vis-NIR setup will consist of three main components: (1) an Agilent Cary 5000 spectrometer, (2) a Harrick Praying Mantis diffuse reflectance attachment, and (3) a Unisoko CoolSpek cryostat attachment. The spectrometer will enable us to collect data over a wide wavelength range, spanning the entire UV to NIR spectrum. The diffuse reflectance attachment will enable us to study MOF reactions with gas-phase substrates (e.g. O2, NO, CO2, CH4) over a wide range of pressures and at high temperatures. The cryostat will enable us to study reactivity patterns of molecular model complexes over a wide temperature range, thereby providing side-by-side comparisons of MOFs vs molecules to elucidate the critical role of the MOF support along with structure/function correlations. Overall, data collected from the UV-Vis-NIR setup will be analyzed in conjunction with data from other techniques currently being pursued in the Harris laboratory, to provide a complete understanding of structure and function in these MOF materials. Finally, the setup will aid in the education of graduate and undergraduate students, through hands-on student training and mentoring, and will generate knowledge to be disseminated throughout the nation at conferences attended by the PI and his group members.