Systematic functionalization of a metal-organic framework via a postsynthetic modification approach.
The pendant amino groups in isoreticular metal-organic framework-3 (IRMOF-3) were subjected to postsynthetic modification with 10 linear alkyl anhydrides (O(CO(CH2)nCH3)2 (where n = 1 to 18) and the extent of conversion, thermal and structural stability, and Brunauer-Emmett-Teller (BET) surface areas of the resulting materials were probed. (1)H NMR of digested samples showed that longer alkyl chain anhydrides resulted in lower conversions of IRMOF-3 to the corresponding amide framework (designated as IRMOF-3-AM2 to IRMOF-3-AM19). Percent conversions ranged from essentially quantitative (approximately 99%, -AM2) to approximately 7% (-AM19) with IRMOF-3 samples. Modified samples were thermally stable up to approximately 430 degrees C and remained crystalline based on powder X-ray diffraction (PXRD) measurements. Under specific reaction conditions, significant conversions were obtained with complete retention of crystallinity, as verified by single-crystal X-ray diffraction experiments. Single crystals of modified IRMOF-3 samples all showed that the F-centered cubic framework was preserved. All single crystals used for X-ray diffraction were analyzed by electrospray ionization mass spectrometry (ESI-MS) to confirm that these frameworks contained the modified 1,4-benzenedicarboxylate ligand. Single crystals of each modified IRMOF-3 were further characterized by measuring the dinitrogen gas sorption of each framework to determine the effects of modification on the porosity of the MOF. BET surface areas (m(2)/g) confirmed that all modified IRMOF-3 samples maintained microporosity regardless of the extent of modification. The surface area of modified MOFs was found to correlate to the size and number of substituents added to the framework.
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, USA.
Kristine K
KK
Tanabe
Zhenqiang
Z
Wang
Seth M
SM
Cohen