A Single‐Molecule‐Level Mechanistic Study of Pd‐Catalyzed and Cu‐Catalyzed Homocoupling of Aryl Bromide on an Au(111) Surface

On‐surface Pd‐ and Cu‐catalyzed C?C coupling reactions between phenyl bromide functionalized porphyrin derivatives on an Au(111) surface have been investigated under ultra‐high vacuum conditions by using scanning tunneling microscopy and kinetic Monte Carlo simulations. We monitored the isothermal reaction kinetics by allowing the reaction to proceed at different temperatures. We discovered that the reactions catalyzed by Pd or Cu can be described as a two‐phase process that involves an initial activation followed by C?C bond formation. However, the distinctive reaction kinetics and the C?C bond‐formation yield associated with the two catalysts account for the different reaction mechanisms: the initial activation phase is the rate‐limiting step for the Cu‐catalyzed reaction at all temperatures tested, whereas the later phase of C?C formation is the rate‐limiting step for the Pd‐catalyzed reaction at high temperature. Analysis of rate constants of the Pd‐catalyzed reactions allowed us to determine its activation energy as (0.41±0.03) eV.     

Supramolecular surface-confined architectures created by self-assembly of triangular phenylene-ethynylene macrocycles via van der Waals interaction

At the liquid/graphite interface triangular and rhombic phenylene-ethynylene macrocycles substituted by alkyl chains self-assemble to form porous two-dimensional (2D) molecular networks of honeycomb and Kagomé types, respectively, or close-packed non-porous structures via alkyl chain interdigitation as the directional intermolecular linkages. Factors that affect the formation of the 2D molecular networks, such as alkyl chain length, solvent, solute concentration, and co-adsorption of guest molecules, were elucidated through a systematic study. For the porous networks, various molecules and molecular clusters were adsorbed in the pores reflecting the size and shape complementarity, exploring a new field of 2D host-guest chemistry.