Reactivity of a model of B₃P₃-doped nanographene with up to three CO₂ molecules

The reactivity of a B₃P₃-doped hexa-cata-hexabenzocoronene, as a model of nanographene (B₃P₃-NG), towards carbon dioxide was studied at the DFT M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G* level of theory. This compound can be classified as a poly-cyclic poly-Frustrated Lewis Pair (FLP) system, as it presents more than one Lewis Acid/Lewis Base pair on its surface, making the capture of several carbon dioxide molecules possible. Two scenarios were considered to fully characterize the capture of CO₂ by this multi-FLP system: (i) fixation of three CO₂ molecules sequentially one by one; and (ii) simultaneous contact of three CO₂ molecules with the B₃P₃-NG surface. The resulting adducts were analyzed as function of activation barriers and the relative stability of the CO₂ capture. A cooperativity effect due to the π-delocalization of the hexa-cata-hexabenzocoronene is observed. The fixation of a CO₂ molecule modifies the electronic properties. It enhances the capture of additional CO₂ molecules by changing the acidy and basicity of the rest of the boron and phosphorus atoms in the B₃P₃-NG system.