In Situ Investigation of Multicomponent MOF Crystallization during Rapid Continuous Flow Synthesis

• Brandon He^a,b
• Lauren K. Macreadie^c,d
• James Gardiner^b
• Shane G. Telfer^d
• Matthew R. Hill*^a,b

• ^aDepartment of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia
• ^bCSIRO Private Bag 10, Clayton South, VIC 3169, Australia
• ^c,School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia
• ^dMacDiarmid Institute for Advanced Materials and Nanotechnology Institute of Fundamental Sciences, Massey University, Palmerston North 4442, New Zealand

Access to the potential applications of metal–organic frameworks (MOFs) depends on rapid fabrication. While there have been advances in the large-scale production of single-component MOFs, rapid synthesis of multicomponent MOFs presents greater challenges. Multicomponent systems subjected to rapid synthesis conditions have the opportunity to form separate kinetic phases that are each built up using just one linker. We sought to investigate whether continuous flow chemistry could be adapted to the rapid formation of multicomponent MOFs, exploring the UMCM-1 and MUF-77 series. Surprisingly, phase pure, highly crystalline multicomponent materials emerge under these conditions. To explore this, in situ WAXS was undertaken to gain an understanding of the formation mechanisms at play during flow synthesis. Key differences were found between the ternary UMCM-1 and the quaternary MUF-7, and key details about how the MOFs form were then uncovered. Counterintuitively, despite consisting of just two ligands UMCM-1 proceeds via MOF-5, whereas MUF-7 consists of three ligands but is generated directly from the reaction mixture. By taking advantage of the scalable high-quality materials produced, C6 separations were achieved in breakthrough settings.

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