2024-03-28T14:05:50Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1315152022-03-07T12:36:01Zcom_10261_10252com_10261_3com_10261_115col_10261_10253col_10261_368
2016-04-28T09:29:41Z
urn:hdl:10261/131515
Orbital redistribution in molecular nanostructures mediated by metal-organic bonds
Yang, Zecyhao
Corso, Martina
Robles, Roberto
Franke, K. J.
Pascual, José I.
Freie Universität Berlin
Ministerio de Economía y Competitividad (España)
Alexander von Humboldt Foundation
China Scholarship Council
German Research Foundation
Oligothiophene
Scanning tunneling microscopy
Atomic force microscopy
Metal−organic coordination
Molecular orbital alignment
Molecular orbital distribution
Dicyanovinyl-quinquethiophene (DCV5T-Me2) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me2 self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me2 lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites.
2016-04-28T09:29:41Z
2016-04-28T09:29:41Z
2014
2016-04-28T09:29:41Z
artículo
ACS Nano 8(10): 10715-10722 (2014)
http://hdl.handle.net/10261/131515
10.1021/nn504431e
http://dx.doi.org/10.13039/501100007537
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/100005156
http://dx.doi.org/10.13039/501100004543
http://dx.doi.org/10.13039/501100001659
eng
Sí
closedAccess
American Chemical Society