1D Coordination π–d Conjugated Polymers with Distinct Structures Defined by the Choice of the Transition Metal: Towards a New Class of Antiaromatic Macrocycles

Santhini, Vijai M.; Wäckerlin, Christian; Cahlík, Aleš; Ondráček, Martin; Pascal, Simon; Matěj, Adam; Stetsovych, Oleksandr; Mutombo, Pingo; Lazar, Petr; Siri, Olivier; Jelı́nek, Pavel

doi:10.1002/anie.202011462

Cited by 25 publications

(39 citation statements)

References 71 publications

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“…However, this scenario can be ruled out by several observations. Namely, XPS measurements of DABQDI molecules deposited on Au(111) at room temperature show in N 1s region two distinct components corresponding to both -NH2 and − NH groups (see SI Figure S3 in Santhini et al 30 ). Moreover, in very rare instances we observe the formation of short defective chains (see SI Figure 4a), whose AFM contrast is clearly distinct from the straight chain since it shows a characteristic "x-like" feature in between the molecular units.…”

Section: Resultsmentioning

confidence: 99%

Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains

et al. 2021

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In hydrogen bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implications remains elusive, leaving opportunities for deeper understanding to harness their fascinating properties.We studied hydrogen-bonded one-dimensional quinonediimine molecular networks which may adopt two isomeric electronic configurations via proton transfer. Herein, we demonstrate that concerted proton transfer promotes a delocalization of π-electrons along the molecular chain, which enhances the cohesive energy between molecular units, increasing the mechanical stability of the chain and giving rise to new electronic in-gap states localized at the ends.

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Section: Resultsmentioning

confidence: 99%

Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains

et al. 2021

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“…The presence of only one peak O 1s at 531.4 eV (CO*) and the disappearance of the C–O*H peak at 533.4 eV evidence the twofold dehydrogenation of SqA and the formation of squarate (Sq). As for dehydrogenation of free-base porphyrins and porphyrinoids, ,− carboxylic acids, ,, as well as other ligands , on copper surfaces, Sq forms coordination compounds with Cu adatoms, such that a CuSq layer forms. In all cases, the C/O ratio agrees well with the expected stoichiometry of 1:1 (Table S1).…”

Section: Resultsmentioning

confidence: 99%

Autocatalytic Surface Explosion Chemistry of 2D Metal–Organic Frameworks

Wäckerlin

Ernst

2021

J. Phys. Chem. C

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Metal–organic frameworks are a combination of inorganic constituents and organic ligands with a high degree of variability which are, as coordination compounds in homogeneous catalysis, potentially highly selective heterogeneous catalysts. The synthesis and thermal stability of monolayer thin Cu-, Ni-, and Fe-squarate 2D MOFs are studied using X-ray photoelectron spectroscopy, scanning tunneling microscopy, and temperature-programmed reaction spectroscopy on a Cu(100) surface in ultrahigh vacuum. Highly ordered 2D squarate MOFs are obtained by mild annealing of squarate multilayers. Upon annealing at higher temperatures, the Ni- and Fe-squarate layers undergo autocatalytic surface explosion chemistry with carbon monoxide as a desorbing product in a very narrow temperature interval. Despite the different stabilities of Ni- and Fe-based MOFs, mixed {Ni + Fe}-MOFs also decompose in a narrow single temperature interval. Such autocatalytic behavior is explained by a numerical model whichunlike rate equation-based kineticsexplicitly considers the chemical nature of nearest neighbors.

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“…[21][22][23] Contemporarily to the progress made in the synthesis of 𝜋-conjugated systems on surfaces, the fabrication of low dimensional coordinative metal-organic nanoarchitectures based on metal ions and 𝜋-conjugated ligands has been extensively explored. [24][25][26][27][28] Herein, the on-surface chemistry toolbox of 𝜋-d systems, achieved by direct deposition of molecular ligands that coordinate with substrate adatoms or by codeposition of different metals and ligands, leading to the hybridization of the d-orbitals of transition metals and frontier orbitals of conjugated ligands, has been extensively investigated.…”

Section: Introductionmentioning

confidence: 99%

Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

et al. 2022

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On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr 2 ) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.

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1D Coordination π–d Conjugated Polymers with Distinct Structures Defined by the Choice of the Transition Metal: Towards a New Class of Antiaromatic Macrocycles

Cited by 25 publications

References 71 publications

Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains

Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains

Autocatalytic Surface Explosion Chemistry of 2D Metal–Organic Frameworks

Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

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