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On-Surface Isomerization of Indigo within 1D Coordination Polymers
Hongxiang Xu1, Ritam Chakraborty2, Abhishek Kumar Adak2,3
1Technical University of Munich, TUM School of Natural Sciences, Physics Department E20, James Franck Strasse 1, 85748, Garching, Germany.
Natural dyes like indigo and Tyrian purple were used to engineer coordination polymers on silver surfaces. These advanced materials show unique configurations and bonding, demonstrating post-synthetic isomerization in nanosystems.
Area of Science:
- Materials Science
- Supramolecular Chemistry
- Surface Science
Background:
- Natural products offer sustainable building blocks for advanced materials.
- Metallosupramolecular engineering enables precise control over material properties.
Purpose of the Study:
- To engineer coordination polymers using natural dyes (indigo, Tyrian purple) on silver surfaces.
- To investigate the atomic structure and bonding of these polymers.
- To explore thermally induced isomerization in interfacial nanosystems.
Main Methods:
- Surface-confined synthesis of coordination polymers.
- Atomic characterization using scanning tunneling microscopy and atomic force microscopy.
- X-ray photoelectron spectroscopy for surface analysis.
- Density functional theory (DFT) calculations.
Main Results:
- Identical coordination polymers with (1 dehydroindigo:1 Fe) repeat units formed on Ag(100) and Ag(111).
- Trans-dehydroindigo exhibited N,O-chelation on both surfaces.
- Isomerization to cis-configuration occurred on Ag(111), leading to N,N- and O,O-chelation.
- DFT confirmed energetic favorability of cis-polymers on Ag(111) and trans-polymers on Ag(100).
Conclusions:
- Demonstrated successful surface-confined metallosupramolecular engineering using natural dyes.
- Revealed post-synthetic linker isomerization in interfacial metal-organic nanosystems.
- Highlighted the role of surface properties in controlling molecular configurations and bonding.
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