Conformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins

Knecht, Peter; Reichert, Joachim; Deimel, P.; Feulner, P.; Haag, Felix; Allegretti, Francesco; Garnica, Manuela; Schwarz, Martin; Auwärter, Willi; Ryan, Paul T. P.; Lee, Tien‐Lin; Duncan, David A.; Seitsonen, Ari P.; Barth, Johannes V.; Papageorgiou, Anthoula C.

doi:10.1002/ange.202104075

Cited by 5 publications

(4 citation statements)

References 45 publications

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“…It is therefore reasonable to assign this component to IMe desorption from the transported Ru‐TPP molecules and to the reintegration of those Ru‐TPP molecules back into the compressed phase. This is in good accord with the stronger binding of ligands to the Ru‐TPP adlayer vs. to Ru‐TPP in direct contact with Ag(111) observed experimentally for CO [14e] . Indeed, DFT calculations find an energy difference of 1.05 eV between the bond strength of IMe to the isolated Ru‐TPP molecule vs. to Ru‐TPP adsorbed on Ag(111).…”

Section: Resultssupporting

confidence: 84%

“…The trans ‐effect is documented upon ligation of several inorganic molecules on metalloporphyrins and phthalocyanines. In particular, a substantial structural trans ‐effect is observed on the Ru‐TPP/Ag(111) upon CO ligation: the Ru atoms are displaced 0.6 Å further away from the Ag interface, while they remain very close to their initial adsorption sites [14e] . In contrast, the strong registry on Ag(111) hollow sites is not found after IMe ligation in the DFT optimised geometries (Figure S4).…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, the strong registry on Ag(111) hollow sites is not found after IMe ligation in the DFT optimised geometries (Figure S4). And, importantly, it is notable that such a porter effect cannot be observed on the corresponding LEED experiment when CO replaces IMe (Figure S11), in an experiment albeit performed at a 100 K lower temperature required by the lower desorption energy of CO [14e] …”

Section: Resultsmentioning

confidence: 99%

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N‐Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru‐Porphyrins

et al. 2022

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Ru‐porphyrins act as convenient pedestals for the assembly of N‐heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru‐porphyrin monolayer, an extraordinary phenomenon can be observed: Ru‐porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analysed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganisation can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalisation of surfaces with carbenes.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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N‐Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru‐Porphyrins

et al. 2022

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“…[ 1,2 ] The supporting interface further introduces the possibility of catalyzing confined reactions that alter the molecular conformation, e.g., thermally‐activated porphyrin dehydrogenation, and turn out to influence the chemical reactivity and magnetic properties of porphyrin molecules. [ 3–5 ] In this regard molecular devices supported at well‐defined interfaces attainable by covalent on‐surface confined polymerization may further benefit from the improvement of their stability and optoelectronic properties. [ 6,7 ] It was further demonstrated that the single ion configuration is uniform across covalently extended porphyrin structures.…”

Section: Introductionmentioning

confidence: 99%

Tuning Transition Metal‐Containing Molecular Magnets by On‐Surface Polymerization

Baranowski,

Cojocariu,

Schio

et al. 2024

Adv Materials Inter

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Porphyrins are promising multifunctional units particularly interesting for the realization of molecular nanodevices. Their structural variety allows to create precursors suitable for the on‐surface polymerization of porphyrin blocks. The corresponding increased stability and improved transport properties of the formed polymerized molecular nanostructures make them practically worthwhile. For the case of 2D porphyrin materials, the effect of polymerization on the magnetic properties of transition metal ions has not been reported yet. Therefore, details on the properties of an extended covalent nickel tetraphenylporphyrin network formed via Ullmann coupling on the Cu(111) surface are reported. By using photoelectron and absorption spectroscopies together with density functional theory calculations, it is systematically evolving how the functional properties of the Ni centers are changed within a polymerized molecular structure in comparison to single‐molecule nickel tetraphenylporphyrin derivatives that build the 2D molecular network. A model that explains the differences in the electronic and magnetic properties observed for the Ni centers in both structures based on the additional rigidity characteristic of the molecular layer after polymerization is drawn.

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Molecular Symmetry and Art: Visualizing the Near‐Symmetry of Molecules in Piet Mondrian's De Stijl

Kingsbury,

Senge

2024

Angewandte Chemie

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Symmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost – investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors or coordinates, is informative, though far from engaging. Often relationships between chemical structure and derived values are obscured. Taking our inspiration from Piet Mondrian’s Compositions, we have depicted the symmetry information encoded within 3D data as blocks of color, to show clearly how chemical arguments and resultant molecular distortion may contribute to symmetry. Great art gives us a new perspective on the world; as a pastiche, this art may allow us to look at familiar molecules, such as porphyrins, in a new light, understanding how their shape and properties are intertwined.

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Conformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins

Cited by 5 publications

References 45 publications

N‐Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru‐Porphyrins

N‐Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru‐Porphyrins

Tuning Transition Metal‐Containing Molecular Magnets by On‐Surface Polymerization

Molecular Symmetry and Art: Visualizing the Near‐Symmetry of Molecules in Piet Mondrian's De Stijl

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