Journal
CHEMISTRY OF MATERIALS
Volume 31, Issue 9, Pages 3248-3256Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.9b00125
Keywords
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Funding
- ERC Consolidator Grant ELECNANO [766555]
- EC FP7-PEOPLE-2011-COFUND AMAR-OUT II program
- Spanish Ramon and Cajal Program [RYC-2012-11133]
- Spanish Ministerio de Economia y Competitividad [FIS 2013-40667-P, FIS 2015-67287-P]
- Comunidad de Madrid [Y2018/NMT-4783, S2013/MIT-3007, CMS2018/NMT-4321]
- IMDEA Foundation
- Praemium Academie of the Academy of Sciences of the Czech Republic [MEYS LM2015087, GACR 18-09914S]
- Operational Programme Research, Development and Education - European Structural and Investment Funds
- Czech Ministry of Education, Youth and Sports [SOLID21 -CZ.02.1.01/0.0/0.0/16_019/0000760 _Z.02.1.01/0.0/0.0/16019/0000754]
- Severo Ochoa Programme for Centers of Excellence in RD (MINECO) [SEV-2016-0686]
- European Research Council (ERC) [766555] Funding Source: European Research Council (ERC)
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On-surface chemistry in ultrahigh vacuum offers complementary routes for synthesizing molecular complexes that cannot be accessed through standard solution chemistry. The presence of a surface not only imposes spatial two-dimensional restraints but also frequently acts as a source of adatoms actively participating in the chemical reactions. Here we demonstrate the formation of gold porphyrin derivatives via thermally induced chemical transformations of a fluorinated free-base porphyrin, 2H-4FTPP, on a Au(111) surface, which can rarely be accessed via standard solution chemistry protocols. We also provide an accurate description of the mechanisms of on-surface reactions and self-assembly processes, including structural and electronic characterization of intermediates and products using high-resolution scanning probe microscopy with a CO tip supported by a computational study. An initial annealing step at 500 K induces planarization of the adsorbed free base via dehydrogenation and ring-closing reactions that preserve the integrity of the C-F bonds. A second annealing step at 575 K enables metalation, producing unprecedented surface-supported gold-coordinated planarized porphyrins. A final annealing step at 625 K induces C-F and C-H activation, leading to intermolecular C-C coupling between phenyl termini to form planarized porphyrin oligomers. These results open new avenues for engineering in a stepwise manner thermally sensitive on-surface chemical reactions and metal-organic compounds that cannot be accessed in solution chemistry.
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