cg8b00238_si_001.pdf (479.79 kB)
Computational Structure Prediction of (4,4)-Connected Copper Paddle-wheel-based MOFs: Influence of Ligand Functionalization on the Topological Preference
journal contribution
posted on 2018-04-05, 00:00 authored by Sarawoot Impeng, Ruel Cedeno, Johannes P. Dürholt, Rochus Schmid, Sareeya BureekaewThe
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.