Developing isocyanide based linkers for the reticular syntheses of low-valent metal coordination networks is a novel turn for the MOF community. Access to a library of multitopic isocyanide ligands from the modified (CNArMes2)2 (ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H3) ligand permitted the systematic study of structural and physical properties of several Ni(0) MOF materials. This includes ditopic isocyanide ligands that have increased length caused by phenyl linkers creating greater pore size in the MOF. As well as a tritopic isocyanide ligand that changed the geometry and topology of the MOF. All of the isocyanide ligands were synthesized via Suzuki-Miyaura coupling of the para-bromo aniline p-BrArMes2NH2 and the para-pinacol boronic ester aniline p-BPinArMes2NH2 . After formylation of the dianiline and dehydration of the diformamide, the diisocyanide ligand is obtained. The sterically hindering m-terphenyl substituent on the isocyanide allows for the preparation of coordinatively unsaturated, low-valent metal centers, such as nickel zero. Due to the extra strength provided from the ligand these MOFs demonstrate stability that leads to the coordination networks’ robustness. Moreover, the dimer and trimer complexes with these same isocyanide ligands have also been synthesized for comparison to their extended counterparts. The MOF systems were studied through crystallography, ATR-IR and gas sorption measurements.

Development of coordinatively unsaturated, low-valent metal isocyanide MOFs

253rd National Meeting (2017)

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