There has been significant recent interests in microp  orous o  rganic p  olymeric (POP) materials due to their potential applications in gas storage and release, chemical separations, and catalysis. One of the most exciting recent developments has been the synthesis of POPs possessing extraordinarily high surface areas via the Yamamoto-Ullmann cross-coupling of tetrakis(4-bromophenyl)methane monomers. These PAF materials (PAF = p  orous a  romatic f  rameworks) have been approximately formulated as diamondoid networks with tetrahedral nodes and simple (unsubstituted) biphenyl units as struts. Although PAF-1 and its derivatives have shown impressive adsorption capacities for H2 and CH4, the absence of functional groups, however, renders them relatively nonspecific as sorbents for small, functionalized molecules. To remedy this deficiency, we have synthesized functionalized PAF-1 derivatives through a de novo approach, starting with CH3-, CH2OH-, and phthalimide-substituted tetrakis(4-bromophenyl)methane building units. The PAF-1-CH2-phthalimide derivative can readily undergo cleavage through hydrazinolysis to generate an aminomethyl derivative, PAF-1-CH2NH2, which can subsequently be converted to an imine derivative. The imine-, alcohol- and amine-functionalized PAF-1 derivatives all exhibit enhanced CO2 uptake (70, 67, and 98 cm3g-1 respectively) and isosteric heats of adsorption (Qst) (18.2, 19.3, and 57.6 kJ mol-1 respectively) relative to the parent PAF-1 system (55 cm3g-1and 15.6 kJ mol-1). Given the extensive use of alcohol- and amine-based p  ost-s  ynthesis ,m  ofidication (PSM) in the related area of MOF chemistry, PAF-1-CH2OH, and PAF-1-CH2NH2 can readily serve as platforms for incorporating site-specific functionalities for many applications.

Functionalized porous aromatic frameworks (PAFs) for CO<sub>2</sub> capture

245th National Meeting (2013)

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Functionalized porous aromatic frameworks (PAFs) for CO2 capture

Functionalized porous aromatic frameworks (PAFs) for CO₂ capture