Direct synthesis of dilithium tetraphenylporphyrin: facile reaction of a free-base porphyrin with vapor-deposited lithium

Schöniger, Maik; Kachel, Stefan R.; Herritsch, Jan; Schröder, Philipp; Hutter, Mark; Gottfried, J. Michael

doi:10.1039/c9cc07170a

Cited by 9 publications

(11 citation statements)

References 28 publications

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“…Over the past decades we have witnessed an intense interest in utilizing porphyrins on surfaces as functional building blocks with a myriad of possible applications: ranging from atomic switches to single‐molecule magnets and catalysts. [1] The surface chemistry of cyclic tetrapyrrole compounds is therefore a topic of extended research [2] and includes the on‐surface metallation [3] as well as s‐block [4] and p‐block [5] element functionalisation. In this context, the effect of the macrocycle substituents has been studied systematically.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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We assess the crucial role of tetrapyrrole flexibility in the CO ligation to distinct Ru-porphyrins supported on an atomistically well-defined Ag(111) substrate.O ur systematic real-space visualisation and manipulation experiments with scanning tunnelling microscopyd irectly probe the ligation, while bond-resolving atomic force microscopya nd X-ray standing-wave measurements characterise the geometry,X-ray and ultraviolet photoelectron spectroscopyt he electronic structure,a nd temperature-programmed desorption the binding strength. Density-functional-theory calculations provide additional insight into the functional interface.W eu nambiguously demonstrate that the substituents regulate the interfacial conformational adaptability,e ither promoting or obstructing the uptake of axial CO adducts.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…Over the past decades we have witnessed an intense interest in utilizing porphyrins on surfaces as functional building blocks with am yriad of possible applications:r anging from atomic switches to single-molecule magnets and catalysts. [1] Thes urface chemistry of cyclic tetrapyrrole compounds is therefore atopic of extended research [2] and includes the onsurface metallation [3] as well as s-block [4] and p-block [5] element functionalisation. In this context, the effect of the macrocycle substituents has been studied systematically.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…Porphyrins are naturally occurring small molecules at the heart of vital biological processes. Their tetrapyrrole ring can host and stabilize on interfaces a large number of the elements of the periodic table, most commonly transition metals, − and also p-block elements as well as alkali metals, offering unique possibilities of tunable functionalization of chemical, optical, and magnetic properties. With the ability of introducing a wide variety of substituents in their periphery, metalloporphyrins are posited as prototypical building blocks of functional interfaces .…”

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confidence: 99%

Tunable Interface of Ruthenium Porphyrins and Silver

et al. 2021

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The adsorption and monolayer self-assembly of functional metal–organic blocks on solid surfaces are critical for the physicochemical properties of these low-dimensional materials. Although modern microscopy tools are very sensitive to the lateral arrangement of such blocks, they are still unable to offer directly the complete structural analysis especially for nonplanar molecules containing different atoms. Here, we apply a combinatorial approach for the characterization of such interfaces, which enables unexpected insights. An archetypal metalloporphyrin on a catalytically active surface as a function of its molecular coverage and substituent arrangement is characterized by low-energy electron diffraction, scanning probe microscopy, X-ray photoelectron spectroscopy, normal-incidence X-ray standing waves, and density functional theory. We look into Ru tetraphenyl porphyrin (Ru-TPP) on Ag(111), which is also converted into its planarized derivates via surface-assisted cyclodehydrogenation reactions. Depending on the arrangement of the phenyl substituents, the Ru atoms have distinct electronic structures and the porphyrin macrocycles adapt differently to the surface: saddle shape (pristine Ru-TPP) or bowl shape (planarized Ru-TPP derivates). In all cases, the Ru atom resides close to the surface (2.59/2.45 Å), preferably located at hollow sites and in the interface between the plane of the porphyrin macrocycle and the Ag surface. For the more flexible pristine Ru-TPP, we identify an additional self-assembled structure, allowing the molecular density of the self-assembled monolayer to be tuned within ∼20%. This precise analysis is central to harnessing the potential of metalloporphyrin/metal interfaces in functional systems.

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Direct synthesis of dilithium tetraphenylporphyrin: facile reaction of a free-base porphyrin with vapor-deposited lithium

Abstract: A dilithium porphyrin was synthesized by vapor-deposition of metallic lithium onto solid free-base porphyrin.

Cited by 9 publications

References 28 publications

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

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

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

Tunable Interface of Ruthenium Porphyrins and Silver

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