Utilizing Nearest-Neighbor Interactions To Alter Charge Transport Mechanisms in Molecular Assemblies of Porphyrins on Surfaces

Schuckman, Amanda E.; Ewers, Bradley W.; Yu, Lam H.; Tomé, João P. C.; Pérez, Lisa M.; Drain, Charles Michael; Kushmerick, James G.; Batteas, James D.

doi:10.1021/acs.jpcc.5b01223

Cited by 17 publications

(32 citation statements)

References 86 publications

(138 reference statements)

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“…We have shown 50,177 that click chemistry can be used to append thioalkyl tethers which can be attached to the Au surface for rapid assessment of chain length and dye association (Fig. 27).…”

Section: Substituted Fluorinated Porphyrinoids For Application In Matmentioning

confidence: 99%

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

et al. 2016

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Porphyrinoids are robust heterocyclic dyes studied extensively for their applications in medicine and as photonic materials because of their tunable photophysical properties, diverse means of modifying the periphery, and the ability to chelate most transition metals. Commercial applications include their use as phthalocyanine dyes in optical discs, porphyrins in photodynamic therapy, and as oxygen sensors. Most applications of these dyes require exocyclic moieties to improve solubility, target diseases, modulate photophysical properties, or direct the self-organization into architectures with desired photonic properties. The synthesis of the porphyrinoid depends on the desired application, but the de novo synthesis often involves several steps, is time consuming, and results in low isolated yields. Thus, the application of core porphyrinoid platforms that can be rapidly and efficiently modified to evaluate new molecular architectures allows researchers to focus on the design concepts rather than the synthesis methods, and opens porphyrinoid chemistry to a broader scientific community. We have focused on several widely available, commercially viable porphyrinoids as platforms: meso-perfluorophenylporphyrin, perfluoro-phthalocyanine, and meso-perfluorophenylcorrole. The perfluorophenylporphyrin is readily converted to the chlorin, bacteriochlorin, and isobacteriochlorin. Derivatives of all six of these core platforms can be efficiently and controllably made via mild nucleophilic aromatic substitution reactions using primary S, N, and O nucleophiles bearing a wide variety of functional groups. The remaining fluoro groups enhance the photo and oxidative stability of the dyes and can serve as spectroscopic signatures to characterize the compounds or in imaging applications using 19F NMR. This review provides an overview of the chemistry of fluorinated porphyrinoids that are being used as a platform to create libraries of photo-active compounds for applications in medicine and materials.

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Section: Substituted Fluorinated Porphyrinoids For Application In Matmentioning

confidence: 99%

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

et al. 2016

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“…[33] It is also noticeable from Figure 7a nd Figures S10a-c that the peak current is almost proportional to n,d emonstratingt hat intra-or intermolecular electron hopping fromt he second to the first layer is faster than electron transfer to the electrode, and therefore extremely efficient. [33] It is also noticeable from Figure 7a nd Figures S10a-c that the peak current is almost proportional to n,d emonstratingt hat intra-or intermolecular electron hopping fromt he second to the first layer is faster than electron transfer to the electrode, and therefore extremely efficient.…”

Section: Ultrafast Electron Transfermentioning

confidence: 79%

A Rotaxane Scaffold Bearing Multiple Redox Centers: Synthesis, Surface Modification and Electrochemical Properties

Steffenhagen

Latus

Trinh

et al. 2018

Chemistry A European J

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A rotaxane scaffold incorporating two dithiolane anchoring units for the modification of gold surfaces has been functionalized with multiple copies of a redox unit, namely ferrocene. Surface modification has been first assessed at the single molecule level by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) imaging, while tip enhanced Raman spectroscopy (TERS) provided the local vibrational signature of the ferrocenyl subunits of the rotaxanes grafted onto the gold surface. Finally, oxidation of the redox moieties within a rotaxane scaffold grafted onto gold microelectrodes has been investigated by ultrafast cyclic voltammetry. Intramolecular electron hopping is indeed extremely fast in this system. Moreover, the kinetics of charge injection depends on the molecular coverage due to the influence of intermolecular contacts on molecular motions.

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“…21 Studies were reported by Schuckman et al of the charge transport properties of a tethered Zn(II) porphyrin thiol complex, tripyridyl porphyrin, in which molecular clusters were inserted within an alkanethiol matrix on Au(111). 22,23 …”

Section: Introductionmentioning

confidence: 99%

Distance-Dependent Measurements of the Conductance of Porphyrin Nanorods Studied with Conductive Probe Atomic Force Microscopy

et al. 2017

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Protocols for nanopatterning porphyrins on Au(111) were developed based on immersion particle lithography. Porphyrins with and without a central metal ion, 5,10,15,20-tetraphenyl-21H,23H-porphyrin (TPP) and 5,10,15,20-tetraphenyl-21H,23H-porphyrin cobalt(II) (CoTPP), were selected for study, which spontaneously formed nanorod geometries depending on concentration parameters. The elongated shapes of the nanorods offers an opportunity for successive distance-dependent conductive probe atomic force microscopy (CP-AFM) measurements along the length of the nanorods. To prepare patterns of TPP and CoTPP nanorods, a mask of silica mesospheres was placed on gold substrates to generate nanoholes within an alkanethiol matrix film. The nanoholes prepared by particle lithography with an immersion step were backfilled with porphyrins by a second immersion step. By controlling the concentration and immersion interval, nanorods of porphyrins were generated with one end of the nanostructure attached to gold within a nanohole. The porphyrin nanorods exhibited slight differences in dimensions at the nanoscale to enable size-dependent measurements of conductive properties. The conductivity along the horizontal direction of the nanorods was evaluated with CP-AFM studies. Changes in conductivity were measured along the long axis of TPP and CoTPP nanorods. The TPP nanorods exhibited conductive profiles of an insulating material, and the CoTPP nanorods exhibited profiles of a semiconductor. The experiments demonstrate the applicability of particle lithography for preparing unique and functional surface platforms of porphyrins to measure distance-dependent conductive properties on gold.

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Utilizing Nearest-Neighbor Interactions To Alter Charge Transport Mechanisms in Molecular Assemblies of Porphyrins on Surfaces

Abstract: This document includes details on the synthesis of the molecule used in this study and its associate characterization along with additional details on the monolayer characterization by FTIR and XPS and additional details on the DFT calculations employed.

Cited by 17 publications

References 86 publications

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

A Rotaxane Scaffold Bearing Multiple Redox Centers: Synthesis, Surface Modification and Electrochemical Properties

Distance-Dependent Measurements of the Conductance of Porphyrin Nanorods Studied with Conductive Probe Atomic Force Microscopy

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