Microscopic Evidence of the Metalation of a Free‐Base Porphyrin Monolayer with Iron

Büchner, Florian; Schwald, Veronika; Comanici, Karmen; Steinrück, Hans‐Peter; Marbach, Hubertus

doi:10.1002/cphc.200600698

Cited by 94 publications

(133 citation statements)

References 22 publications

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“…Such molecules are not directly visible as individual molecules in the STM under the actual imaging conditions due to their high mobility. [61][62][63] The observed effective phase separation of 2HTPP and CoTPP on Cu (111) results from the fact that the adsorption of the free base 2HTPP is dominated by molecule-substrate interactions, while the supramolecular arrangement of CoTPP is caused by attractive molecule-molecule interactions. Fig.…”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

“…4,32,35,36,56,58,[72][73][74][75][76][77][78][79][80][81][82][83][84][85] It is nowadays well established that metalloporphyrins can be synthesised readily on a metal surface by the reaction of a corresponding free base porphyrin with an ''available'' metal atom. The respective metal atom can be provided on the surface by pre-or postdeposition, or originate from the surface itself.…”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

“…Depending on the metal, this in situ metalation can proceed already at room temperature or after moderate annealing. 72,73,83 It was studied in detail for 2HTPP with Co, 4 …”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

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Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Marbach

Steinrück

2014

Chem. Commun.

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Scanning tunnelling microscopy (STM) enables us to directly observe the dynamic behaviour of organic molecules on surfaces. While imaging atoms and molecules using STM is certainly fascinating by itself, corresponding temperature-dependent measurements allow for the quantitative determination of the energetics and kinetics of the underlying molecular surface processes. Herein, we review recent advances in the STM investigation of the dynamic behaviour of adsorbed porphyrins at and close to room temperature.Three different case studies are discussed, providing insight into the dynamics of diffusion, rotation, reaction, and molecular switching at surfaces, based on isothermal STM measurements. The reviewed examples demonstrate that variable temperature STM can be a suitable tool to directly monitor the dynamic behaviour of individual adsorbed molecules, at and close to room temperature. Free base porphyrins on Cu(111) proved to be particularly suitable for these studies due to the strong bonding interaction between the iminic nitrogen atoms in the porphyrin macrocycle and the Cu substrate atoms. As a consequence, the corresponding activation energies for surface diffusion, self-metalation reaction and conformational switching are of a magnitude that allows for monitoring the processes at and around room temperature, in contrast to most previous studies, which were performed at cryogenic temperatures. The kinetic analysis of the surface diffusion and self-metalation was performed using an Arrhenius approach, yielding the corresponding activation energies and preexponential factors. In contrast, the conformational switching process was analysed in the framework of transition state theory, based on the Eyring equation. This approach provides a more detailed insight into interpretable thermodynamic potentials, i.e., the enthalpic and entropic contributions to the activation barrier. The analysis shows that at room temperature the adsorption and switching behaviour of the investigated free base porphyrin on Cu(111) is dominated by entropic effects. Since the entropic energy contribution vanishes at low temperatures, the importance of experiments conducted at temperatures close to room temperature is emphasized.

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Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

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Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Marbach

Steinrück

2014

Chem. Commun.

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“…The formation of cobalt (II) and iron (II) tetraphenylporphyrins (MTPP's, M = Co, Fe) from the direct reaction of the bare metal atoms (Co or Fe) and adsorbed tetraphenylporphyrin (2H-TPP) molecules have been reported authors [16,17]. The adsorbed porphyrin monolayer efficiently metallated in situ under clean UHV conditions by evaporation onto the metal atoms which increase the possibility to study metalloporphyrins using surface science techniques at low sample temperatures.…”

Section: Isrn Analytical Chemistrymentioning

confidence: 99%

“…Pure Fe-tetraphenylporphyrin (Fe-TPP) was produced under UHV conditions by in situ metalation of free-base 2H-5, 10, 15, 20-tetraphenylporphyrin (2H-TPP) monolayers with Fe atoms deposited by an electron beam evaporator [17]. STM micrographs showed the appearance of intramolecular protrusions consequent to Fe evaporation and the evidence of the TPP metalation.…”

Section: Isrn Analytical Chemistrymentioning

confidence: 99%

Electronic Structure of 2H-Tetraphenylporphyrin at Fe/Si (100) Interface

Lal

Jain

2013

ISRN Analytical Chemistry

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Many recent studies have highlighted the possibility to tailor the physical and chemical properties of porphyrin at the molecular level to design novel catalysts, sensors and devices with applications in electronics, opto-electronics, and so forth. In the present work, we study the electronic properties of 2H-Tetraphenylporphyrin (2H-TPP) on iron (Fe) and iron silicide (Fe 3 Si) onto Si (100) substrate using X-ray and Ultraviolet photoelectron spectroscopy (XPS & UPS). The results revealed that the iron atom is coordinated by TPP molecules on Fe/Si as well as on Fe 3 Si/Si. XPS results provide evidence of the iron coordination with TPP molecules. The UPS analysis evidenced the fine structure in the electronic spectra related to HOMO states below the Fermi level.

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Synthese und Manipulation rotierbarer Cer‐Porphyrin‐Sandwichkomplexe auf einer Oberfläche

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Microscopic Evidence of the Metalation of a Free‐Base Porphyrin Monolayer with Iron

Cited by 94 publications

References 22 publications

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Electronic Structure of 2H-Tetraphenylporphyrin at Fe/Si (100) Interface

Synthese und Manipulation rotierbarer Cer‐Porphyrin‐Sandwichkomplexe auf einer Oberfläche

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