Metalloporphyrin Molecular Sieves Based on Tin(IV)porphyrin Phenolates

Fallon, Gary D.; Lee, Marcia A.-P.; Langford, Steven J.; Nichols, Peter J.

doi:10.1021/ol025935u

Cited by 39 publications

(25 citation statements)

References 34 publications

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“…E int then decreases with increasing coverage and becomes attractive (E int < 0) above q % 0.45, as shown in Figure 6 c. Unlike in the case of C 70 , it is not possible to fit the experimental data with a constant interaction parameter. Similar trends have also been reported in theoretical calculations of self-diffusivities in zeolites: as shown by Krishna et al, [26] CH 4 , Ar, or Ne in ITE-type zeolites at 298 K can be interpreted within the quasichemical approach using a linearly decreasing interaction energy [Eq. (7)].…”

Section: Coverage-dependent Hopping Ratessupporting

confidence: 83%

Adsorption and Dynamics of Long‐Range Interacting Fullerenes in a Flexible, Two‐Dimensional, Nanoporous Porphyrin Network

Kiebele¹,

Bonifazi²,

Cheng³

et al. 2006

ChemPhysChem

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Herein, a detailed investigation of the adsorption and dynamics of C60 and C70 fullerenes hosted in a self-assembled, two-dimensional, nanoporous porphyrin network on a solid Ag surface is presented. Time-resolved scanning tunneling microscopy (STM) studies of these supramolecular systems at the molecular scale reveal distinct host-guest interactions giving rise to a pronounced dissimilar mobility of the two fullerenes within the porphyrin network. Furthermore, long-range coverage-dependent interactions between the all-carbon guests, which clearly affect their mobility and are likely mediated by a complex mechanism involving the Ag substrate and the flexible porphyrin host network, are observed. At increased fullerene coverage, this unprecedented interplay results in the formation of large fullerene chains and islands. By applying a lattice gas model with nearest-neighbor interactions and by evaluating the fullerene-pair distribution functions, the respective coverage-dependent guest-guest interaction energies are estimated.

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Section: Coverage-dependent Hopping Ratessupporting

confidence: 83%

Adsorption and Dynamics of Long‐Range Interacting Fullerenes in a Flexible, Two‐Dimensional, Nanoporous Porphyrin Network

Kiebele¹,

Bonifazi²,

Cheng³

et al. 2006

ChemPhysChem

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“…Their chemical versatility and structural similarity to zeolites makes them promising candidates for the fabrication of multifunctional materials with various potential applications as catalysts, molecular sieves, and chemical sensors. [7][8][9] Among the vast series of functional organic molecules, metalloporphyrins and their derivatives have proved to be exceedingly useful building blocks for the construction of supramolecular functional networks as a result of their excellent thermal and chemical stability and synthetic versatility. In particular, their peripheral functionalities at the meso and b positions can be chemically modified for the engineering of a variety of extended supramolecular networks through selected intermolecular interactions, such as van der Waals and hydrogen bonding or metal-centered coordination.…”

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confidence: 99%

“…Using such an approach, numerous porphyrin-based three-dimensional (3D) architectures both in solution and the solid state with remarkable affinities toward selected molecular guests have been reported. [7,9] However, on solid surfaces mainly single porphyrin molecules and close-packed, self-assembled monolayers (MLs) have been investigated so far.[10-13] 2D superficial networks showing defined cavities with hosting capabilities have not been described previously. Herein, we report on the first successful preparation of a 2D porphyrin-based supramolecular assembly featuring a porous network structure on a single crystal metal surface.…”

mentioning

confidence: 99%

A Two‐Dimensional Porphyrin‐Based Porous Network Featuring Communicating Cavities for the Templated Complexation of Fullerenes

Spillmann

Kiebele

Stöhr³

et al. 2006

Advanced Materials

189

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The self-assembly of molecular species on surfaces has been widely employed to produce well-defined, two-dimensional (2D) porous organic, inorganic, and metal-organic networks. [1][2][3][4][5] Such regular networks offer the possibility to arrange functional units like atoms or molecules in a repetitive and spatially ordered arrangement. Thus, these networks serve as templates for the controlled self-assembly of singlemolecule-based devices, which will be of use in future nanotechnological applications.[6]Specifically, nanoporous phases consisting of metal-organic materials are increasingly attracting interest in materials chemistry. Their chemical versatility and structural similarity to zeolites makes them promising candidates for the fabrication of multifunctional materials with various potential applications as catalysts, molecular sieves, and chemical sensors. [7][8][9] Among the vast series of functional organic molecules, metalloporphyrins and their derivatives have proved to be exceedingly useful building blocks for the construction of supramolecular functional networks as a result of their excellent thermal and chemical stability and synthetic versatility. In particular, their peripheral functionalities at the meso and b positions can be chemically modified for the engineering of a variety of extended supramolecular networks through selected intermolecular interactions, such as van der Waals and hydrogen bonding or metal-centered coordination. Using such an approach, numerous porphyrin-based three-dimensional (3D) architectures both in solution and the solid state with remarkable affinities toward selected molecular guests have been reported. [7,9] However, on solid surfaces mainly single porphyrin molecules and close-packed, self-assembled monolayers (MLs) have been investigated so far.[10-13] 2D superficial networks showing defined cavities with hosting capabilities have not been described previously. Herein, we report on the first successful preparation of a 2D porphyrin-based supramolecular assembly featuring a porous network structure on a single crystal metal surface. Scanning tunneling microscopy (STM) studies show that porphyrin 1 (Fig. 1a) self-organizes into an ordered porous molecular ML upon vapor deposition on a Ag(111) surface (Fig. 1b). Subsequent codeposition of C 60 molecules results in the selective inclusion of the fullerenes within the cavities. Unusually, the fullerene guest molecules show a distinct interaction over distances longer than the van der Waals radii, as evidenced from the formation of long fullerene chains and 2D arrays. Time-lapse imaging experiments additionally reveal that the weak physisorptive interactions between hosts and guests allow single C 60 molecules to displace themselves to neighboring pores by thermal activation at 298 K. Figure 1. a) Chemical structure of the porphyrin derivative 1 investigated in this study [26]. Note that the 3,5-di(tert-butyl)phenyl and the 3-cyanophenyl substituents feature a certain conformational flexibility with respect to the ce...

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“…In terms of light absorption, glasses that have been surface-modified to produce thin layers of porphyrinic arrays should also be compatible with the strong light absorption properties of the same porphyrinic materials, i.e., allowing 100% of visible light to be absorbed by the porphyrin chromophore. We have been investigating the condensation of bis(hydroxy)tin(IV) porphyrins with a range of structurally varied phenols and carboxylic acids to produce both discrete multiporphyrin assemblies and supramolecular arrays [5][6][7][8].…”

mentioning

confidence: 99%