Observation of phase evolution in porphyrinic Zr metal-organic frameworks

In accordance with our preliminary results, the porphyrinic Zr metal-organic frameworks (MOFs), display a distinct phase evolution on modulated solvo-thermal synthesis, in which the undercoordinated PCN-222 framework first forms and then transforms into the fully coordinated PCN-223. In this proposed experiment we which to validate our hypothesis based on the PCN-222 being the kinetically favoured form, whilst the PCN-223 is the thermodynamically stable polymorph, all the while acquiring mechanistic insights into the formation of both frameworks and the phase transformation itself. To this end, we will perform XANES/EXAFS-PDF-PXRD analysis, on multiple length-scale as a function of time, in operando conditions. The expected outcomes will shed light on the phase behaviour and ultimately enable the better design of reaction conditions for each polymorph.