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Title: Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111)

For combined low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) study, we investigate self-assembly of the dipolar nonplanar organic semiconductor chloro boron-subphthalocyanine (ClB-SubPc) on Cu(111). We also observe multiple distinct adsorption configurations and demonstrate that these can only be understood by taking surface-catalyzed dechlorination into account. A detailed investigation of possible adsorption configurations and the comparison of experimental and computational STM images demonstrates that the configurations correspond to “Cl-up” molecules with the B–Cl moiety pointing toward the vacuum side of the interface, and dechlorinated molecules. In contrast to the standard interpretation of adsorption of nonplanar molecules in the phthalocyanine family, we find no evidence for “Cl-down” molecules where the B–Cl moiety would be pointing toward the Cu surface. We show computationally that such a configuration is unstable and thus is highly unlikely to occur for ClB-SubPc on Cu(111). Moreover, using these assignments, we discuss the different self-assembly motifs in the submonolayer coverage regime. The combination of DFT and STM is essential to gain a full atomistic understanding of the surface–molecule interactions, and our findings imply that phthalocyanines may undergo surface-catalyzed reactions hitherto not considered. Also, our results indicate that care has to be taken when analyzing possible adsorptionmore » configurations of polar members of the phthalocyanine family, especially when they are adsorbed on comparably reactive surfaces like Cu(111).« less
 [1] ;  [2] ;  [3] ;  [3] ;  [2] ;  [4] ;  [2] ;  [1]
  1. Univ. of Arizona, Tucson, AZ (United States)
  2. Graz Univ. of Technology (Austria)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Nebraska, Lincoln, NE (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 1932-7447; KC0403020
Grant/Contract Number:
SC00112704; SC0012704
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 13; Journal ID: ISSN 1932-7447
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1260162