Unravelling the conductance path through single-porphyrin junctions

Abbassi, Maria El; Zwick, Patrick; Rates, Alfredo; Stefani, Davide; Prescimone, Alessandro; Mayor, Marcel; Zant, Herre S. J. van der; Dulić, Diana

doi:10.1039/c9sc02497b

Cited by 32 publications

(48 citation statements)

References 26 publications

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“…11. Heterocyclic derivatives include carbazole (15a), 137 dibenzothiophene (15b), 137 dibenzofuran (15c), 137 benzodifuran (16), 142,143 benzodithiophene (17), 66 bithiophene (18), 68 and (metallo-)porphyrins (19); [144][145][146] example structures are shown in Fig. 12.…”

Section: Structural Diversity Of Oaesmentioning

confidence: 99%

A review of oligo(arylene ethynylene) derivatives in molecular junctions

O’Driscoll

Bryce

2021

Nanoscale

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Section: Structural Diversity Of Oaesmentioning

confidence: 99%

A review of oligo(arylene ethynylene) derivatives in molecular junctions

O’Driscoll

Bryce

2021

Nanoscale

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“…Metalloporphyrins have been extensively studied as molecular wires owing to a number of appealing properties such as high chemical stability and conjugation, modular metal center and rich supramolecular chemistry . Metalloporphyrins have been chemically connected to metal electrodes either by directly lying flat on the metal surfaces via π‐orbital interactions between the metal and the porphyrin ring, or by covalent electrode/molecule attachment through porphyrin ring substituents . Although the latter results in a robust, straightforward method to wire oligo‐porphyrins between two electrodes, the inclusion of such anchoring Scheme precludes the exploitation of other sources of supramolecular interactions that might lead to the formation of more efficient electron pathways already exploited in the natural biomolecular homologous wire.…”

Section: Introductionmentioning

confidence: 99%

Tuning Single‐Molecule Conductance in Metalloporphyrin‐Based Wires via Supramolecular Interactions

et al. 2020

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Nature hasd eveloped supramolecular constructs to delivero utstanding charge-transport capabilities usingm etalloporphyrin-baseds upramoleculara rrays. Herein we incorporate simple,n aturally inspired supramolecular interactions via theaxial complexation of metalloporphyrinsintothe formation of as ingle-molecule wire in an anoscale gap. Smalls tructural changesi nt he axialc oordinatingl inkers result in dramatic changesi nt he transportp ropertieso ft he metalloporphyrinbasedw ire. Thei ncreased flexibilityo fapyridine-4-yl-methanethiol ligand duet oa ne xtra methyl group, as compared to am orer igid 4-pyridinethioll inker, allows thep yridine-4-ylmethanethiol ligand to adopta nu nexpectedh ighlyc onductive stackeds tructure betweent he twoj unctione lectrodesa nd the metalloporphyrin ring.D FT calculations reveal am olecular junction structurec omposedo fashifteds tack of thet wo pyridiniclinkers andthe metalloporphyrin ring.Incontrast, the more rigid4-mercaptopyridineligandpresentsamore classical lifted octahedral coordinationo ft he metalloporphyrin metal center,l eading to al ongere lectronp athway of lowerc onductance. This worksopens to supramolecular electronics, aconcept alreadyexploited in naturalorganisms.

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“…Furthermore, mechanical stabilization involving van der Waals forces between metallic electrode and molecule may also lead to metastable junction configurations. 39 It is thus not straightforward to associate a conductance peak with a specific electron path because of the complexity of the peak distribution. To be able to identify the metastable peptide conformation corresponding to each extracted conductance, complementary electronic structure computations will be required.…”

Section: Resultsmentioning

confidence: 99%