Following the Metalation Process of Protoporphyrin IX with Metal Substrate Atoms at Room Temperature

González-Moreno, Rubén; Sánchez‐Sánchez, Carlos; Trelka, Marta; Otero, Roberto; Cossaro, Albano; Verdini, Alberto; Floreano, Luca; Ruíz-Bermejo, Marta; García-Lekue, Aran; Martín‐Gago, José A.; Rogero, Celia

doi:10.1021/jp200533a

Cited by 65 publications

(110 citation statements)

References 33 publications

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“…35,36,58,[79][80][81][82] As discussed in the last section, the adsorption behaviour of 2HTPP and metalloporphyrins (e.g., CoTPP), is very different, see Fig. 2.…”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 94%

“…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%

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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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“…35,36,58,[79][80][81][82] As discussed in the last section, the adsorption behaviour of 2HTPP and metalloporphyrins (e.g., CoTPP), is very different, see Fig. 2.…”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 94%

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

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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confidence: 99%

“…Based on a combined scanning tunnelling microscopy and X-ray photoelectron spectroscopy study we present detailed insights into pronounced changes of long-range order and intramolecular conformation during the self-metalation of 10,15, to CuTTBPP on Cu(111).…”

mentioning

confidence: 99%

“…6 The metalation can occur with predeposited and postdeposited metal atoms, or via the so-called self-metalation with atoms from an underlying metal substrate. [7][8][9][10] Thereby, the free base porphyrin picks up a substrate atom and reacts to the corresponding metalloporphyrin with the release of hydrogen. Herein, we report on the self-metalation of 2HTTBPP on Cu(111), which goes along with a massive intramolecular conformational change due to reduced molecule-substrate interactions.…”

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confidence: 99%

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Massive conformational changes during thermally induced self-metalation of 2H-tetrakis-(3,5-di-tert-butyl)-phenylporphyrin on Cu(111)

et al. 2014

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Based on a combined scanning tunnelling microscopy and X-ray photoelectron spectroscopy study we present detailed insights into pronounced changes of long-range order and intramolecular conformation during the self-metalation of 10,15, to CuTTBPP on Cu(111).Upon metalation, the porphyrin literally ''pops up'' from the surface, due to a drastically reduced molecule-substrate interaction.A detailed understanding of the adsorption behaviour of molecular building blocks on solid surfaces is a crucial step towards the bottom-up fabrication of functional devices.1,2 Scanning tunnelling microscopy (STM) is an especially suitable method to study the relevant elementary processes. Porphyrins are regarded as prototype functional molecular building blocks for nanotechnology applications. Recent surface science studies of porphyrins addressed their switching capabilities 3-5 and adsorption behaviour as well as surface-mediated metalation of free base porphyrins. 6 The metalation can occur with predeposited and postdeposited metal atoms, or via the so-called self-metalation with atoms from an underlying metal substrate. 7-10 Thereby, the free base porphyrin picks up a substrate atom and reacts to the corresponding metalloporphyrin with the release of hydrogen. Herein, we report on the self-metalation of 2HTTBPP on Cu(111), which goes along with a massive intramolecular conformational change due to reduced molecule-substrate interactions. In a vivid image, this process can be summarized as a popping up of the molecular centre from the surface. The investigation of free base porphyrins on single crystal Cu surfaces recently received great interest, mainly due to the very strong attractive interactions of the iminic nitrogen atoms of the porphyrin macrocycle with Cu atoms from the substrate. 11-15This interactions can give rise to very peculiar adsorption behaviours like the one observed by STM for 2HTTBPP on Cu(111), see Fig. 1a. The corresponding supramolecular structure exhibits a bimodal appearance, i.e. alternating bright and dark rows, which (predominantly) consist of convex and concave intramolecular conformations, respectively (see also Fig. 3a-h and discussion below).

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The Growth of Organic Nanomaterials by Molecular Self‐Assembly at Solid Surfaces

Gallego¹,

Otero²,

Miranda³

2013

Organic Nanomaterials

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Following the Metalation Process of Protoporphyrin IX with Metal Substrate Atoms at Room Temperature

Cited by 65 publications

References 33 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

Massive conformational changes during thermally induced self-metalation of 2H-tetrakis-(3,5-di-tert-butyl)-phenylporphyrin on Cu(111)

The Growth of Organic Nanomaterials by Molecular Self‐Assembly at Solid Surfaces

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