On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth
Abstract Ullmann‐type coupling is the most widely used on‐surface reaction to form rationally designed bottom‐up molecular nanoarchitectures. A commonly observed reaction product in this reaction is an organometallic phase, however little is known about the formation of this phase. The on‐surface po...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-02-01
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| Series: | Advanced Materials Interfaces |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/admi.202300728 |
| _version_ | 1797329466888814592 |
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| author | R.S. Koen Houtsma Jeanne vanZuilen Meike Stöhr |
| author_facet | R.S. Koen Houtsma Jeanne vanZuilen Meike Stöhr |
| author_sort | R.S. Koen Houtsma |
| collection | DOAJ |
| description | Abstract Ullmann‐type coupling is the most widely used on‐surface reaction to form rationally designed bottom‐up molecular nanoarchitectures. A commonly observed reaction product in this reaction is an organometallic phase, however little is known about the formation of this phase. The on‐surface polymerization of the prochiral precursor 6,12‐dibromochrysene (DBCh) on Ag(111) is studied. Upon annealing of DBCh on Ag(111), a linear organometallic polymer forms. However, the delicate energy balance involved in the polymerization of DBCh is such that, at room temperature, several reaction intermediates, which eventually lead to the formation of the organometallic polymer, can be observed experimentally. Organometallic monomers, dimers, and trimers are finds, that self‐assemble into distinct networks. The experimental availability of these reaction intermediates provides key insights into the formation of the organometallic polymer. Comparing the chirality of the intermediates and the polymer sheds additional light on the reaction mechanism leading to the formation of the polymer. The main finding is that the organometallic polymer is not formed by a simple coupling of the reaction intermediates, but rather requires the breaking and re‐establishing of the C─Ag bonds. Additionally, a Br‐enhanced growth mode is observed, where the split‐off halogens align the polymers, which results in an increased polymer length. |
| first_indexed | 2024-03-08T07:06:00Z |
| format | Article |
| id | doaj.art-afa0cf1283114555a064e047a52f51bc |
| institution | Directory Open Access Journal |
| issn | 2196-7350 |
| language | English |
| last_indexed | 2024-03-08T07:06:00Z |
| publishDate | 2024-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Advanced Materials Interfaces |
| spelling | doaj.art-afa0cf1283114555a064e047a52f51bc2024-02-03T04:45:28ZengWiley-VCHAdvanced Materials Interfaces2196-73502024-02-01114n/an/a10.1002/admi.202300728On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer GrowthR.S. Koen Houtsma0Jeanne vanZuilen1Meike Stöhr2Zernike Institute for Advanced Materials University of Groningen Nijenborgh 4 Groningen 9747AG the NetherlandsZernike Institute for Advanced Materials University of Groningen Nijenborgh 4 Groningen 9747AG the NetherlandsZernike Institute for Advanced Materials University of Groningen Nijenborgh 4 Groningen 9747AG the NetherlandsAbstract Ullmann‐type coupling is the most widely used on‐surface reaction to form rationally designed bottom‐up molecular nanoarchitectures. A commonly observed reaction product in this reaction is an organometallic phase, however little is known about the formation of this phase. The on‐surface polymerization of the prochiral precursor 6,12‐dibromochrysene (DBCh) on Ag(111) is studied. Upon annealing of DBCh on Ag(111), a linear organometallic polymer forms. However, the delicate energy balance involved in the polymerization of DBCh is such that, at room temperature, several reaction intermediates, which eventually lead to the formation of the organometallic polymer, can be observed experimentally. Organometallic monomers, dimers, and trimers are finds, that self‐assemble into distinct networks. The experimental availability of these reaction intermediates provides key insights into the formation of the organometallic polymer. Comparing the chirality of the intermediates and the polymer sheds additional light on the reaction mechanism leading to the formation of the polymer. The main finding is that the organometallic polymer is not formed by a simple coupling of the reaction intermediates, but rather requires the breaking and re‐establishing of the C─Ag bonds. Additionally, a Br‐enhanced growth mode is observed, where the split‐off halogens align the polymers, which results in an increased polymer length.https://doi.org/10.1002/admi.202300728graphene nanoribbonsmetal‐ligand interactionson‐surface synthesisreaction intermediatesscanning tunneling microscopyUllmann coupling |
| spellingShingle | R.S. Koen Houtsma Jeanne vanZuilen Meike Stöhr On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth Advanced Materials Interfaces graphene nanoribbons metal‐ligand interactions on‐surface synthesis reaction intermediates scanning tunneling microscopy Ullmann coupling |
| title | On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth |
| title_full | On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth |
| title_fullStr | On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth |
| title_full_unstemmed | On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth |
| title_short | On‐Surface Ullmann‐Type Coupling: Reaction Intermediates and Organometallic Polymer Growth |
| title_sort | on surface ullmann type coupling reaction intermediates and organometallic polymer growth |
| topic | graphene nanoribbons metal‐ligand interactions on‐surface synthesis reaction intermediates scanning tunneling microscopy Ullmann coupling |
| url | https://doi.org/10.1002/admi.202300728 |
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