Fluorocarbon-Functionalized Superhydrophobic Metal-Organic Framework: Enhanced CO₂ Uptake via Photoinduced...

The design and synthesis of porous materials for selective capture of CO₂ in the presence of water vapor is of paramount importance in the context of practical separation of CO₂ from the flue gas stream. Here, we report the synthesis and structural characterization of a photoresponsive fluorinated MOF {[Cd(bpee)(hfbba)]·EtOH} (1) constructed by using 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (hfbba), Cd(NO₃)₂, and 1,2-bis(4-pyridyl)ethylene (bpee) as building units. Due to the presence of the fluoroalkyl -CF₃ functionality, compound 1 exhibits superhydrophobicity, which is validated by both water vapor adsorption and contact angle measurements (152°). The parallel arrangement of the bpee linkers makes compound 1 a photoresponsive material that transforms to {[Cd₂(rctt-tpcb)(hfbba)₂]·2EtOH} (rctt-tpcb = regio cis,trans,trans-tetrakis(4-pyridyl)cyclobutane; 1IR) after a [2 + 2] cycloaddition reaction. The photomodified framework 1IR exhibits increased uptake of CO₂ in comparison to 1 under ambient conditions due to alteration of the pore surface that leads to additional weak electron donor-acceptor interactions with the -CF₃ groups, as examined through periodic density functional theory calculations. The enhanced uptake is also aided by an expansion of the pore window, which contributes to increasing the rotational entropy of CO₂, as demonstrated through force field based free energy calculations.