• Riss, Alexander
• Chakraborty, Ritam
• Papageorgiou, Anthoula
• Adak, Abhishek Kumar
• Xu, Hongxiang
• Reichert, Joachim
• Meier, Dennis
• Narasimhan, Shobhana
• Das, Arpan
• Barth, Jv

Abstract

<jats:title>Abstract</jats:title><jats:p>Natural products are attractive components to tailor environmentally friendly advanced new materials. We present surface‐confined metallosupramolecular engineering of coordination polymers using natural dyes as molecular building blocks: indigo and the related Tyrian purple. Both building blocks yield identical, well‐defined coordination polymers composed of (1 dehydroindigo : 1 Fe) repeat units on two different silver single crystal surfaces. These polymers are characterized atomically by submolecular resolution scanning tunnelling microscopy, bond‐resolving atomic force microscopy and X‐ray photoelectron spectroscopy. On Ag(100) and on Ag(111), the <jats:italic>trans</jats:italic> configuration of dehydroindigo results in N,O‐chelation in the polymer chains. On the more inert Ag(111) surface, the molecules additionally undergo thermally induced isomerization from the <jats:italic>trans</jats:italic> to the <jats:italic>cis</jats:italic> configuration and afford N,N‐ plus O,O‐chelation. Density functional theory calculations confirm that the coordination polymers of the <jats:italic>cis</jats:italic>‐isomers on Ag(111) and of the <jats:italic>trans</jats:italic>‐isomers on Ag(100) are energetically favoured. Our results demonstrate post‐synthetic linker isomerization in interfacial metal‐organic nanosystems.</jats:p>

Topics

• density
• surface
• polymer
• single crystal
• silver
• theory
• atomic force microscopy
• density functional theory
• photoelectron spectroscopy
• chemical ionisation