Spatiotemporal Design of the Metal-Organic Framework DUT-8(M)

Switchable metal-organic frameworks change their structure in time and selectively open their pores adsorbing guest molecules, leading to highly selective separation, pressure amplification, sensing and actuation applications. The three-dimensional engineering of metal-organic frameworks has reached a high level of maturity, but spatiotemporal evolution opens a new perspective towards engineering materials in the 4th dimension (time) by t-axis design, in essence exploiting the deliberate tuning of activation barriers. This work demonstrates the first example in which an explicit temporal engineering of a switchable metal-organic framework (DUT-8, M1M2(ndc)2dabco, ndc = 2,6,-naphthalenedicarboxylate, dabco = 1,4 diazabicyclo[2.2.2]octane, M1 = Ni, M2 = Co) is presented. The temporal response is deliberately tuned by variation of cobalt content. We present a spectrum of advanced analytical methods for analyzing the switching kinetics stimulated by vapor adsorption using in situ time resolved techniques ranging from ensemble adsorption and advanced synchrotron X-ray diffraction experiments to individual crystal analysis. A novel analysis technique based on microscopic observation of individual crystals in a microfluidic channel reveals the lowest limit for adsorption switching reported so far. The time constants for the bulk ensembles range from 2 - 300 s. Differences in spatiotemporal response of crystal ensembles originate from a delay (induction) time that varies statistically and widens characteristically with increasing cobalt content reflecting increasing activation barriers.