On-surface transmetalation of metalloporphyrins

Hötger, Diana; Abufager, Paula; Morchutt, Claudius; Alexa, Patrick; Grumelli, Doris; Dreiser, Jan; Stepanow, Sebastian; Gambardella, Pietro; Busnengo, H. F.; Etzkorn, Markus; Gutzler, Rico; Kern, Klaus

doi:10.1039/c8nr04786c

Cited by 25 publications

(30 citation statements)

References 47 publications

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“…This redox transmetalation is described in detail in ref. 25 and has been reported for porphyrins, 26 phthalocyanines, 27 and pyrphyrins. 28 The polarization curve of FeTPyP + Co/Au(111) catalysing ORR is depicted in Fig.…”

Section: Resultsmentioning

confidence: 82%

“…13 This leaves the Fe centre undercoordinated and accessible as catalytically active site for OXR. The deposition of Co to the FeTPyP layer leads to a partial exchange of the Fe in the macrocycle with Co, 25 yielding a mixed bimetallic network with Fe and Co coordinated within the macrocycle as well as coordinated to the peripheral pyridyl groups on the molecule. 13 The transmetalation occurs as a spontaneous process at room temperature during the deposition of Co onto FeTPyP.…”

Section: Resultsmentioning

confidence: 99%

“…This is masked by the Fe that is expulsed from the porphyrin macrocycle, which sits between molecule and Au(111) substrate and exhibits a featureless XAS signal due to the missing ligand field provided by the pyrrolic nitrogen. 25 The resulting weak XLD signal is further reduced after ORR (Fig. 5b), presumably due to the reorganisation into disordered structures that do not allow Fe or Co coordination at the peripheral pyridyl groups.…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media

Hötger

Etzkorn

Morchutt

et al. 2019

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media

Hötger

Etzkorn

Morchutt

et al. 2019

Phys. Chem. Chem. Phys.

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“…Metalation routes. Several metalation routes can be exploited at surfaces in UHV (figure 15) [28], including physical vapor deposition (PVD), self-metalation, tip manipulation, and chemical vapor deposition (CVD) [24,25,28,29,80,[84][85][86][87][88][89][90][91]. For PVD, both free-base macrocycles and single metal atoms are deposited on a supporting surface, and temperature-dependent metalation occurs, in some cases even at ambient temperature Table 1.…”

Section: Metalationmentioning

confidence: 99%

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

Vesselli

2020

J. Phys. Mater.

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Many complex mechanisms underlying the fascinating functionalities provided by tetrapyrrolic macrocycles in biochemistry have been already unraveled. Light harvesting, molecular transport, and catalytic conversion are some of the processes performed by tetrapyrrole-based centers embedded in protein pockets. The main function is determined by the single atom species that is caged in the macrocycle, while a finer tuning (band gap, chemical selectivity etc) is granted by the geometric and electronic structure of the tetrapyrrole, including its residues, and by the proximal and distal structures of the protein surroundings that exploit the molecular trans-effect and direct weak interactions, respectively. Hence, a scientific and technological challenge consists in the artificial replication of both structure and functionality of natural reaction centers in 2D ordered arrays at surfaces. Nano-architected 2D metalorganic frameworks can be indeed self-assembled under controlled conditions at supporting surfaces and, in the specific, porphyrin-and phthalocyaninebased systems have been widely investigated in ultra-high vacuum conditions by means of surface science approaches. Deep insight into the geometry, electronic structure, magnetic properties, ligand adsorption mechanisms, and light absorption has been obtained, with the strong experimental constraint of vacuum. Especially in the case of the interaction of tetrapyrroles with ligands, this limit represents a relevant gap with respect to both comparison with natural counterparts from the liquid environment and potential applicative views at both solid-liquid and solid-gas interfaces. Thus, a step forward in the direction of near-ambient pressure is strongly necessary, while maintaining the atomiclevel detail characterization accuracy. Nowadays this becomes feasible by exploiting state-of-the-art experimental techniques, in combination with computational simulations. This review focusses on the latest advances in this direction.

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“…Due to their structural flexibility, meso-substituted porphyrin molecules interact with surface adatoms on metallic substrates. Hötger et al [84] studied the surface transmetalation of central metals in TPP and TPyP molecules on Au(111) surface. They reported that Fe +2 cation of FeTPP can be replaced by Co in a redox transmetalation-like reaction on Au(111) surface.…”

Section: Conformational Studies Of Meso-substituted Porphyrins On Submentioning

confidence: 99%

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

2020

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Porphyrins are fascinating molecules with applications spanning various scientific fields. In this review we present the use of periodic density functional theory (PDFT) calculations to study the structure, electronic properties, and reactivity of porphyrins on ordered two dimensional surfaces and in the formation of nanostructures. The focus of the review is to describe the application of PDFT calculations for bridging the gaps in experimental studies on porphyrin nanostructures and self-assembly on 2D surfaces. A survey of different DFT functionals used to study the porphyrin-based system as well as their advantages and disadvantages in studying these systems is presented.

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On-surface transmetalation of metalloporphyrins

Abstract: Experimental and computational data sheds light onto the metal exchange in porphyrin monolayers.

Cited by 25 publications

References 47 publications

Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media

Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

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