Aggregation and Contingent Metal/Surface Reactivity of 1,3,8,10‐Tetraazaperopyrene (TAPP) on Cu(111)

Abstract

The structural chemistry and reactivity of 1,3,8,10-tetraazaperopyrene (TAPP) on Cu(111) under ultra-high-vacuum (UHV) conditions has been studied by a combination of experimental techniques (scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy, XPS) and DFT calculations. Depending on the deposition conditions, TAPP forms three main assemblies, which result from initial submonolayer coverages based on different intermolecular interactions: a close-packed assembly similar to a projection of the bulk structure of TAPP, in which the molecules interact mainly through van der Waals (vDW) forces and weak hydrogen bonds; a porous copper surface coordination network; and covalently linked molecular chains. The Cu substrate is of crucial importance in determining the structures of the aggregates and available reaction channels on the surface, both in the formation of the porous network for which it provides the Cu atoms for surface metal coordination and in the covalent coupling of the TAPP molecules at elevated temperature. Apart from their role in the kinetics of surface transformations, the available metal adatoms may also profoundly influence the thermodynamics of transformations by coordination to the reaction product, as shown in this work for the case of the Cu-decorated covalent poly(TAPP-Cu) chains.

Homo-coupling of terminal alkynes on a noble metal surface

“…In this way, not only the local electrostatic potential of the atoms, but also screening of the core-hole in the final state is taken into account when simulating the core-level shifts. Similar calculations yielded reasonable results and proved to be helpful for the understanding of bonding properties in surface anchoring of organic species 57 and on-surface molecular architectures 58 .…”

Temperature-dependent self-assembly of NC–Ph5–CN molecules on Cu(111)

“…The adatom concentration results from an equilibrium between detachment and attachment processes from kink sites, and depends on the temperature, on the energy barrier for detachment and diffusion, and on the step and kink density. Formation of Cu-coordinated bonds for deposition 12,15,18,25,43 or annealing 17,28 at room temperature has been reported for several kinds of molecules on Cu(111).…”

“…14,22,23 At sufficiently high temperature, however, copper substrates can spontaneously supply adatoms for coordination, as reported for molecules containing pyridyl groups on Cu(100) 13,24 and on Cu(111). 15,[25][26][27] On Cu(111), Cu coordination or hydrogen bond formation occurs depending on deposition temperature for a N-substituted derivative of pyrene, 28,29 for molecules containing pyridyl groups, 26 and for a carbonitrile-modified anthracene species. 17 The question whether the molecules may play an active role in the atom detachment from steps has emerged.…”

“…17 The question whether the molecules may play an active role in the atom detachment from steps has emerged. 18,28 Also, the influence of the deposition rate on the assembly outcome was investigated for trinitrile molecules. 18 On Ag(111), dicarbonitrile-polyphenyls (NC-Ph n -CN, with n = 3 − 6) and Co adatoms form metal-organic honeycomb networks.…”

Rhodizonic Acid on Noble Metals: Surface Reactivity and Coordination Chemistry

“…[15][16][17][18] Notably, a wide variety of different molecules, including 1,3,5-tris(4-mercaptophenyl)benzene (TMB), 1,3,8,10-tetrazaperopyrene (TAPP), oxalic acid, among many others deprotonate upon adsorption to crystalline Cu, which for carboxyl groups is known to be catalyzed by the lattice gas of Cu adatoms. [19][20][21] Once deprotonated, molecules often form metal coordination bonds with the present Cu adatoms, which was demonstrated conclusively for trimesic acid (TMA). 15 Some of these molecules require thermal activation in order to deprotonate.…”