Imaging of Single Molecular Behaviors Under Bifurcated Three‐Centered Hydrogen Bonding

Abstract The mechanism for interaction and bonding of single guest molecules with active sites fundamentally determines the sorption and subsequent catalytic processes occurring in host zeolitic frameworks. However, no real‐space studies on these significant issues have been reported thus far, since atomically visualizing guest molecules and recognizing single Al T‐sites in zeolites remain challenging. Here, we atomically resolved single thiophene probes interacting with acid T‐sites in the ZSM‐5 framework to study the bonding behaviors between them. The synergy of bifurcated three‐centered hydrogen bonds and van der Waals interactions can “freeze” the near‐horizontal thiophene and make it stable enough to be imaged. By combining the imaging results with simulations, direct atomic observations enabled us to precisely locate the single Al T‐sites in individual straight channels. Then, we statistically found that the thiophene bonding probability of the T11 site is 15 times higher than that of the T6 site. For different acid T‐sites, the variation in the interaction synergy changes the inner angle of the host–guest O−H⋅⋅⋅S hydrogen bond, thereby affecting the stability of the near‐horizontal thiophene and leading to considerable bonding inhomogeneities.