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The peculiar Au···H hydrogen bonding has garnered significant interests, but its existence and nature remain an open question in gold chemistry. In this paper, we established and authenticated the first intramolecular Au···H-O hydrogen bonding in gold(I) complexes. Our computational results based on an ab initio valence bond (V method, namely the block-localized wave function (BLW) method, clarified that this Au···H-O hydrogen bonding is a new type of resonance-assisted hydrogen bond (RAH. In this RAHB, π conjugation in the hydrogen b
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