Computational NMR Spectra of o-Benzyne and Stable Guests and Their Hemicarceplexes

The incarceration of o‐benzyne and 27 other guest molecules within hemicarcerand 1, as reported experimentally by Warmuth, and Cram and co‐workers, respectively, has been studied by density functional theory (DFT). 1H‐NMR chemical shifts, rotational mobility and conformational preference of the guests within the supramolecular cage were determined, which showed intriguing correlations of the chemical shifts with structural parameters of the host‐guest system. Furthermore, based on the computed chemical shifts reassignments of some NMR signals are proposed. This affects in particular the putative characterization of the volatile benzyne molecule inside a hemicarcerand, for which our CCSD(T) and KT2 results indicate that the experimentally observed signals are most likely not resulting from an isolated benzyne within the supramolecular host. Instead, we show that the guest reacted with an aromatic ring of the host, and this adduct is responsible for the experimentally observed signals The following organizations are thanked for financial support: MICINN (PhD-scholarship ACC CTQ2011-25086/BQU, projects CTQ2014-59212-P, CTQ2015-70851-ERC, CTQ2017-87392-P), CONACyT project 2014-383560, GenCat (PhD scholarship ARR 2015_FI_B_00165, 2014SGR1202 and XRQTC network) and European Fund for Regional Development (FEDER, UNGI10-4E-801)