Computational Structure Prediction of (4,4)-Connected Copper Paddle-wheel-based MOFs: Influence of Ligand Functionalization on the Topological Preference

The effect of linkers with extended π-system on the topological preference of (4,4)-connected copper paddle-wheel-based metal–organic frameworks (MOFs) was investigated using the reverse topological approach (RTA) in which a genetic algorithm (GA) and the DFT-derived force field MOF-FF were used for ranking and predicting the most stable phase. Three tetracarboxylate linkers bearing different functionality, namely, phenylene (L1), naphthalene (L2), and anthracene (L3) groups, were studied. All potential topologies including nbo-b, ssa, ssb, pts, and lvt-b were considered. The computational results reveal that nbo-b is the most stable topology for all three investigated linkers. However, L2 is also formed in ssb according to experimental findings. Our simulation results show that the CH−π interactions with a Y-shaped configuration between naphthalene moieties of L2 stabilize the ssb framework. Unlike L2, CH−π interactions are not favorable for L1 and L3 because of unsuitable size of the π-system. The results of the RTA predictions are in agreement with experimentally reported data, suggesting the capability of RTA for accurate structural predictions of MOFs. More importantly, this work shows the exemption of reticular chemistry in which linker functionalization can result in alteration of the resulting topology, as found in the case of linker L2.