Coordination-Driven Construction of Porphyrin Nanoribbons at a Highly Oriented Pyrolytic Graphite (HOPG)/Liquid Interface

Carvalho, M. Alice; Dekkiche, Hervé; Nagasaki, Mayumi; Kikkawa, Yoshihiro; Ruppert, Romain

doi:10.1021/jacs.9b02145

Cited by 16 publications

(13 citation statements)

References 40 publications

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“…In a later report, nanoribbons were built from symmetrical porphyrins C31.5a – c or C31.5d – e stabilized by either hydrogen bonding between the enaminoketone fragments or by coordination of nickel(II). 624 …”

Section: Macrocyclic Systemsmentioning

confidence: 99%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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Section: Macrocyclic Systemsmentioning

confidence: 99%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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“…15−17 The addition of alkyl chains to phenyl-substituted porphyrins has assisted in the on-surface construction of porphyrin dimers and nanoribbons. 18,19 Peripherally alkylated copper(II) octaalkoxyl-substituted phthalocyanine also form stable SAMs, which is attributed to the higher desorption barrier produced by the alkyl substituents. 20 A series of alkyloxyphenyl-substituted porphyrins were studied by Wang et al, and they found "high stability and close-packed assembly is attributed to van der Waals interactions between the alkyl chains and the graphite substrate, which substantially increases the desorption barrier of the combined molecules".…”

Section: ■ Introductionmentioning

confidence: 99%

“…Representative examples include the following studies. Molecular species such as n -alkylcyanobiphenyl (nCB), porphyrins, and phthalocyanines designed with long alkyl substituents (typically more than eight CH 2 groups), which have little effect on their electronic properties, produce well-defined SAMs on conducting surfaces under ambient conditions. − The addition of alkyl chains to phenyl-substituted porphyrins has assisted in the on-surface construction of porphyrin dimers and nanoribbons. , Peripherally alkylated copper(II) octaalkoxyl-substituted phthalocyanine also form stable SAMs, which is attributed to the higher desorption barrier produced by the alkyl substituents . A series of alkyloxyphenyl-substituted porphyrins were studied by Wang et al, and they found “high stability and close-packed assembly is attributed to van der Waals interactions between the alkyl chains and the graphite substrate, which substantially increases the desorption barrier of the combined molecules” .…”

Section: Introductionmentioning

confidence: 99%

Alkynyl Linkers as a Design Tool to Gain Control over the Self-Assembly of Meso-Substituted Porphyrins on HOPG

et al. 2020

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Self-assembled monolayers (SAMs) fall generally into two broad categories: those that are covalently bound either to the surface or to each other and those that rely on weaker forces such as hydrogen bonding or van der Waals forces. The engineering of the structure of SAMs formed from weaker forces is an exciting and complex field that often utilizes long alkane substituents bound to core moieties. The core provides the unique optical, electronic, or catalytic property desired, while the interdigitation of the alkane chains provides the means for creating well-regulated patterns of cores on the substrate. This design technique sometimes fails because some of the alkane substituents remain extended into solution rather than become interdigitated on the substrate. One contributor to this is steric hindrance between elements of the core and of the alkane chain. It is shown that the use of an alkyne linker between the core and the alkane chain can, in the case of meso-substituted porphyrins, significantly reduce this steric barrier and allow more stable and predictable surface structures to form. In particular, 5,15-bis(1-octynyl)porphyrin and 5,15-bis(1-tetradecynyl)porphyrin are shown to form significantly more stable SAMs than their alkane-linked counterparts. Scanning tunneling microscopy is used to provide detailed surface structures. Temperature and solution concentration dependence of the surface coverage is also reported. Density functional theory (DFT) is used to determine the energetic effects associated with alkane substitution at both the meso and β positions and the beneficial energetic effects of the alkyne linker.

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“…Intrigued by the cooperative reactivity of manganese porphyrins adsorbed at adjacent locations at the solid–liquid interface, we decided to design and synthesize covalently connected metal-porphyrins, with the ultimate aim to investigate with STM the possible cooperativity between two metal centers in the same molecule. Several examples of covalently linked porphyrin dimers have been described [28,29,30,31,32] and some have been imaged with STM in an ultra-high vacuum environment or at a solid–liquid interface [33,34,35,36,37]. Our intention to adsorb porphyrin dimers as immobilized assemblies at a solid–liquid interface required the attachment of long aliphatic chains, which are known to aid assembly as a result of van der Waals interactions with the surface and intermolecular alkane chain interdigitation [38].…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Covalently Linked Porphyrin Dimers at the Solid–Liquid Interface

Habets¹,

Lensen²,

Speller

et al. 2019

Molecules

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The synthesis and surface self-assembly behavior of two types of metal-porphyrin dimers is described. The first dimer type consists of two porphyrins linked via a rigid conjugated spacer, and the second type has an alkyne linker, which allows rotation of the porphyrin moieties with respect to each other. The conjugated dimers were equipped with two copper or two manganese centers, while the flexible dimers allowed a modular built-up that also made the incorporation of two different metal centers possible. The self-assembly of the new porphyrin dimers at a solid–liquid interface was investigated at the single-molecule scale using scanning tunneling microscopy (STM). All dimers formed monolayers, of which the stability and the internal degree of ordering of the molecules depended on the metal centers in the porphyrins. While in all monolayers the dimers were oriented coplanar with respect to the underlying surface (‘face-on’), the flexible dimer containing a manganese and a copper center could be induced, via the application of a voltage pulse in the STM setup, to self-assemble into monolayers in which the porphyrin dimers adopted a non-common perpendicular (‘edge-on’) geometry with respect to the surface.

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Coordination-Driven Construction of Porphyrin Nanoribbons at a Highly Oriented Pyrolytic Graphite (HOPG)/Liquid Interface

Cited by 16 publications

References 40 publications

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Alkynyl Linkers as a Design Tool to Gain Control over the Self-Assembly of Meso-Substituted Porphyrins on HOPG

Self-Assembly of Covalently Linked Porphyrin Dimers at the Solid–Liquid Interface

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