On-Surface Synthesis and Characterization of an Iron Corrole

Schmid, Martin; Zugermeier, Malte; Herritsch, Jan; Klein, Benedikt P.; Krug, Claudio K.; Ruppenthal, Lukas; Müller, Philipp; Kothe, Michael; Schweyen, Peter; Bröring, Martin; Gottfried, J. Michael

doi:10.1021/acs.jpcc.8b00067

Cited by 19 publications

(15 citation statements)

References 49 publications

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“…Sample annealing temperatures were held for 3 min, if not indicated otherwise. 3H-HEDMC was synthesized from the respective didesoxybiladiene by oxidative ring closure according to the literature . The term monolayer is used for a complete monomolecular layer that uniformly covers the surface.…”

Section: Methodsmentioning

confidence: 99%

“…3H-HEDMC was synthesized from the respective didesoxybiladiene by oxidative ring closure according to the literature. 41 The term monolayer is used for a complete monomolecular layer that uniformly covers the surface. In contrast, the unit ML refers to the number of objects (atoms or molecules) per Ag surface atom.…”

Section: ■ Methodsmentioning

confidence: 99%

“…Although many of these applications involve surfaces and interfaces, the interface chemistry of corroles has rarely been addressed. Besides few publications with focus on transition-metal corroles − or corrole dimers, , there is only a small number of studies of free-base corroles on metal surfaces. All of these studies were performed with tris(pentafluorophenyl)corrole. − The pentafluorophenyl substituents exert a strong electron-withdrawing effect and thereby influence the electronic structure of the corrole macrocycle.…”

Section: Introductionmentioning

confidence: 99%

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On-Surface Formation of a Transient Corrole Radical and Aromaticity-Driven Interfacial Electron Transfer

et al. 2020

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Corroles on metal surfaces show substantial reactivity and aromaticity-driven interfacial electron transfer of their transient σ/π-radicals. These effects are much more pronounced than for the closely related porphyrins, as has been demonstrated by using an octaalkylcorrole (2,3,8,12,17, and its singly N− H dehydrogenated product 2H-HEDMC on a Ag(111) surface through a combination of experimental and theoretical methods. 3H-HEDMC assumes a nonplanar adsorption geometry caused by intramolecular steric repulsion between the three N−H hydrogen atoms. One of the N−H bonds is tilted far out of the molecular plane and points toward the surface. This N−H bond undergoes surface-catalyzed and entropy-driven homolytic scission already below 230 K, resulting in the formation of planar, strain-relieved 2H-HEDMC as a formal π-radical with a 17π-electron conjugation path. The experimental N−H bond scission barrier of 74 kJ/mol agrees well with theory. 2H-HEDMC engages in transfer of electron density from the surface to the molecule. The additional electron density quenches the radical spin and leads to aromatic stabilization because it influences the electronic structure toward an aromatic 18π-electron conjugation path. Our study demonstrates that aromaticity considerations are useful to rationalize and predict interfacial electron transfer effects, which play an important role in organic electronics, electrocatalysis, and sensors.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On-Surface Formation of a Transient Corrole Radical and Aromaticity-Driven Interfacial Electron Transfer

et al. 2020

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“…Metal complexes of corrole, the one carbon-short relative of the biologically ubiquitous porphyrins, have been studied extensively over the last two decades [1] and are currently finding their way into applications. [2] A significant number of reports on the use of corroles and metal corroles as modular building blocks in larger supermolecules is now available, with a large structural diversity spanning from sterically encumbered ligand systems [3] over photofunctional oligomers [4] and nanoparticles [5] to surface coatings [6,7] and protein adducts. [8] For this development the availability of readily accessible corroles carrying reactive moieties for (bio)orthogonal reaction schemes is of utmost importance.…”

Section: Introductionmentioning

confidence: 99%

Biometal Corrole Active Esters and Their Amino Acid and Peptide Conjugates

et al. 2020

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The synthesis of a series of A2B‐corroles with 4‐carboxyphenyl substituent is described. The macrocycles are prepared from dipyrromethanes and 4‐formylbenzoic acid under Gryko conditions. Redox active biometal complexes are formed from the corrole carboxylic acids with the metal ions of cobalt, iron, and manganese, but not with copper. From all free corrole bases and metal complexes, the respective active esters are obtained in good yields by condensation with NHS (N‐hydroxysuccinimide) and EDC (1‐ethyl‐3‐dimethylaminopropyl‐carbodiimide). Starting from the active esters of the free corrole bases, the copper corroles are accessible in acceptable yields. Oxidation‐ and spin states of the biometal corroles correspond to those of simple corroles and are confirmed spectroscopically and magnetically. Ethylenediamine is efficiently coupled with the corrole carboxylic acids by EDC, whereby selective two‐fold coupling is observed. For the coupling to NαBoc‐lysine as well as NαFmoc‐lysine the use of corrole active esters is advantageous. The metalation of corroles carrying N‐protected lysine side chains turns out to proceed only with loss of most of the material. Here, the coupling of the amino acid building block with the metal corrole active ester proved to be the synthetically more applicable variant. The resulting NαFmoc‐lysine conjugates of both a free base corrole and a manganese corrole complex are shown to be suitable for use in Merrifield solid phase peptide synthesis.

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“…After metalation, the metal–salophene complex is planar and has a C 2v symmetry. There are four methods to supply the metal for the metalation: one being the so-called self-metalation of organic molecules with atoms from the substrate surface, − the second being metalation with a metal atom from an STM-tip, and the remaining two being the metalation of molecules with either pre- ,− or postdeposited − ,,, metal atoms. We used the last of these methods.…”

Section: Introductionmentioning

confidence: 99%

In Situ Synthesis of Metal–Salophene Complexes on Intercalated Graphene

et al. 2020

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On-surface metalation provides a tool to vary magnetic and electronic properties of metal−organic complexes and produces clean samples of the desired product. We used this technique to metalate 5,5′-dibromosalophene with the 3d transition metals Co, Fe, and Cr on Co-intercalated graphene grown on Ir(111). The metalation process was investigated by X-ray photoelectron spectroscopy (XPS). The electronic structure of the obtained salophene complexes was investigated using a combination of scanning tunneling microscopy and spectroscopy with density functional theory calculations. XPS data show that deposition of the transition metals at 398 K causes the metal atoms to interact with the molecules, while higher temperatures are needed to complete the reaction. Furthermore, we are able to distinguish the three different metal−organic complexes by their electronic structure.

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On-Surface Synthesis and Characterization of an Iron Corrole

Cited by 19 publications

References 49 publications

On-Surface Formation of a Transient Corrole Radical and Aromaticity-Driven Interfacial Electron Transfer

On-Surface Formation of a Transient Corrole Radical and Aromaticity-Driven Interfacial Electron Transfer

Biometal Corrole Active Esters and Their Amino Acid and Peptide Conjugates

In Situ Synthesis of Metal–Salophene Complexes on Intercalated Graphene

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