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Supporting InformationAmerican Chemical Society

The calculated BDE of 5MRs in simplified models 3 N and 3 C The energy units are given in kcal mol 1 Bond energy Bond energy N1 Au4 75 2 C1 Au4 89 6 N1 Au5 78 4 C1 Au5 95 1 C2 Au6 111 6 C2 Au6 110 9 C3 Au7 112 5 N3 Au7 109 5 N8 Au11 75 7 C8 Au11 89 5 N8 Au12 78 4 C8 Au12 95 3

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formed by the sinusoidal 5MRs the contrast observed therecan be only owed to the presence of Rh species confined within these rings Figures 1E G In the models presented in Figure 1G a rectangular unit is marked in yellow that would correspond to the 5 MRs along the 011 and 010 respectively All above C s

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Interestingly preliminary DFT calculations show that the aromaticity in the three 5MRs of these osmatricycles can be easily tuned by the ligand substitution Finally the broad UV/Vis absorption spectra of these novel polycyclic complexes were also reported

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the p osition of 5MRs in the sup er lattice F or 3MRs ak e there are t w o p ossible con gurations the trefoil ak e and 2 the linear con guration The minimization pro cedure is the same The optimal con guration is the trefoil whic h has the shorter p erimeter and the total edge length as w

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