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Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001).

ABSTRACT: Properties of metal oxides, such as optical absorption, can be influenced through the sensitization with molecular species that absorb visible light. Molecular/solid interfaces of this kind are particularly suited for the development and design of emerging hybrid technologies such as dye-sensitized solar cells. A key optimization parameter for such devices is the choice of the compounds in order to control the direction and the intensity of charge transfer across the interface. Here, the deposition of two different molecular dyes, porphyrin and coumarin, as single-layered islands on a NiO(001) single crystal surface have been studied by means of non-contact atomic force microscopy at room temperature. Comparison of both island types reveals different adsorption and packing of each dye, as well as an opposite charge-transfer direction, which has been quantified by Kelvin probe force microscopy measurements.

SUBMITTER: Freund S

PROVIDER: S-EPMC6541355 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

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Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001).

Freund Sara S Hinaut Antoine A Marinakis Nathalie N Constable Edwin C EC Meyer Ernst E Housecroft Catherine E CE Glatzel Thilo T

Beilstein journal of nanotechnology 20190415

Properties of metal oxides, such as optical absorption, can be influenced through the sensitization with molecular species that absorb visible light. Molecular/solid interfaces of this kind are particularly suited for the development and design of emerging hybrid technologies such as dye-sensitized solar cells. A key optimization parameter for such devices is the choice of the compounds in order to control the direction and the intensity of charge transfer across the interface. Here, the deposit ...[more]

PMID: 31165014

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Project description:In recent studies, porphyrin derivatives have been frequently used as building blocks for the fabrication of metal-organic coordination networks (MOCNs) on metal surfaces under ultrahigh vacuum conditions (UHV). The porphyrin core can host a variety of 3d transition metals, which are usually incorporated in solution. However, the replacement of a pre-existing metal atom in the porphyrin core by a different metallic species has been rarely reported under UHV. Herein, we studied the influence of cyanophenyl and pyridyl functional endgroups in the self-assembly of structurally different porphyrin-based MOCNs by the deposition of Fe atoms on tetracyanophenyl (Co-TCNPP) and tetrapyridyl-functionalized (Zn-TPPyP) porphyrins on Au(111) by means of scanning tunneling microscopy (STM). A comparative analysis of the influence of the cyano and pyridyl endgroups on the formation of different in-plane coordination motifs is performed. Each porphyrin derivative formed two structurally different Fe-coordinated MOCNs stabilized by three- and fourfold in-plane coordination nodes, respectively. Interestingly, the codeposited Fe atoms did not only bind to the functional endgroups but also reacted with the porphyrin core of the Zn-substituted porphyrin (Zn-TPyP), i.e., an atom exchange reaction took place in the porphyrin core where the codeposited Fe atoms replaced the Zn atoms. This was evidenced by the appearance of molecules with an enhanced (centered) STM contrast compared with the appearance of Zn-TPyP, which suggested the formation of a new molecular species, i.e., Fe-TPPyP. Furthermore, the porphyrin core of the Co-substituted porphyrin (Co-TCNPP) displayed an off-centered STM contrast after the deposition of Fe atoms, which was attributed to the binding of the Fe atoms on the top site of the Co-substituted porphyrin core. In summary, the deposition of metal atoms onto organic layers can steer the formation of structurally different MOCNs and may replace pre-existing metal atoms contained in the porphyrin core.

Dataset Information

Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001).

Publications

Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001).

Similar Datasets

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