Fluorous organic building blocks were utilized to develop two self-assembled, hydrophobic, fluorinated porous organic polymers (FPOPs), namely, FPOP-100 and FPOP-101. Comprehensive mechanical analyses of these functionalised triazine network polymers marked the introduction of mechanical stiffness among all porous organic network materials; the recorded stiffnesses are analogous to those of their organic-inorganic hybrid polymer congeners, that is, metal-organic frameworks. Furthermore, this study introduces a new paradigm for the simultaneous installation of mechanical stiffness and high surface hydrophobicity into polymeric organic networks, with the potential for transfer among all porous solids. Control experiments with non-fluorinated congeners underlined the key role of fluorine, in particular, bis-trifluoromethyl functionalization in realizing the dual features of mechanical stiffness and superhydrophobicity.
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