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Reentrant facets of gold crystals that should be present according to their Wulff shape are not observed because these concave sites typically grow out due to kinetic considerations. This study demonstrates the significant effect of the crystal facet termination and surface reconstruction of an oxide substrate on the shape of supported gold nanocrystals.The alkylidene double bond configuration of transient ortho-quinone methides (o-QMs) is studied by cryogenic ion trap vibrational spectroscopy. To this end, o-QMs are formed from ortho-hy