New strapped porphyrins as hosts for fullerenes: synthesis and complexation study

Giguère, Jean-Benoît; Morin, Jean‐François

doi:10.1039/c1ob06643a

Cited by 20 publications

(17 citation statements)

References 47 publications

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“…In this example, it has been probed that the -conjugated moieties in the host play a role increasing the binding ability of the system to encapsulate fullerenes. In particular, when the electronic density of the host increase the affinity also increases [305].…”

Section: Supportmentioning

confidence: 96%

Coordination chemistry on carbon surfaces

Axet¹,

Dechy‐Cabaret²,

Durand³

et al. 2016

Coordination Chemistry Reviews

106

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Section: Supportmentioning

confidence: 96%

Coordination chemistry on carbon surfaces

Axet¹,

Dechy‐Cabaret²,

Durand³

et al. 2016

Coordination Chemistry Reviews

106

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“…[28][29][30] For example, "picket-fence" and ansa-like "strapped" designs have been widely used for the preparation of many synthetic metallo-and free-base porphyrin complexes. Ru II -Pors [31] or Fe II -Pors [32,33] that bind O 2 , CO, and/or N 2 mimicking haem-containing proteins have been used in synthetic peptide models [34][35][36] and as chiral catalysts for asymmetric syn-thesis, [37][38][39] Zn II -Pors has been used as a template for rotaxanes, [40] conjugated molecular tapes, [41] a host for fullerene, [42] self-assembled materials, [43][44][45][46] and H 2 -Pors has been used as a multi-dentate polynucleating ligand [47] and template for viologen rotaxanes. [48,49] Because their molecular structures mimic macroscopic objects, many strapped porphyrins have received diverse names such as "gyroscope", "basket handle", "pocket", "picnic basket", "coronet" or "capped".…”

Section: Introductionmentioning

confidence: 99%

Tautomerism and Atropisomerism in Free‐Base (meso)‐Strapped Porphyrins: Static and Dynamic Aspects

Urbani

Torres

2014

Chemistry A European J

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We report herein some outstanding examples of atropisomerism and tautomerism in five (meso-)strapped porphyrins. Porphyrins S0-S4 have been synthesised, characterised and studied in detail by spectroscopic and spectrometric techniques, and their isomeric purity verified by HPLC analysis. In particular, they exhibit perfectly well-defined NMR spectra that display distinct patterns depending on their average symmetry at room temperature: C2v , D2d , C2h , C2v , and D2h for S0-S4, respectively. NH tautomerism was evidenced by variable-low-temperature (1) H NMR experiments in [D2 ]dichloromethane performed on S0 (Δ${G{{{\ne}\hfill \atop {\rm 298K}\hfill}}}$=48±1 kJ mol(-1) ) and S1 (Δ${G{{{\ne}\hfill \atop {\rm 298K}\hfill}}}$=55±3 kJ mol(-1) ), which has led to an understanding of the average spectra observed for the five porphyrins at room temperature. On the other hand, S2 and S3 are stable atropisomers at room temperature, easily separated and characterised, as a result of restricted rotation of their strapped bridges due to their high rotational barrier energies. Upon heating to 82 °C, they slowly equilibrate to a thermodynamic ratio of 64:36 in favour of the more stable S2 isomer. This atropisomerisation process was evidenced by (1) H NMR spectroscopy and monitored by HPLC, from which high rotational energy barriers of 115.2 (Δ${G{{{\ne}\hfill \atop {\rm S2}\rightarrow {\rm S3}\hfill}}}$) and 116.9 kJ mol(-1) (Δ${G{{{\ne}\hfill \atop {\rm S2}\rightarrow {\rm S3}\hfill}}}$) were deduced.

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“…Host platforms containing extended p-systems have been designed because of their affinity towards the sphere-like unsaturated structure of fullerenes. In this line, several covalent or supramolecular approaches pursued include: (a) macrocyclic arene-based receptors [18][19][20][21][22][23][24] , (b) macrocyclic structures containing aromatic heterocycles [25][26][27][28] , (c) p-extended TTF receptors [29][30][31][32][33] and (d) macrocyclic or jawlike structures containing porphyrin moieties 17,[34][35][36][37][38][39][40][41][42][43][44][45] . Interestingly, Fujita and co-workers reported the use of the empty channels of a metal-organic framework (MOF) for encapsulating fullerenes upon soaking MOF crystals in fullerene-containing toluene.…”

mentioning

confidence: 99%

Sponge-like molecular cage for purification of fullerenes

et al. 2014

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Since fullerenes are available in macroscopic quantities from fullerene soot, large efforts have been geared toward designing efficient strategies to obtain highly pure fullerenes, which can be subsequently applied in multiple research fields. Here we present a supramolecular nanocage synthesized by metal-directed self-assembly, which encapsulates fullerenes of different sizes. Direct experimental evidence is provided for the 1:1 encapsulation of C 60 , C 70 , C 76 , C 78 and C 84 , and solid state structures for the host-guest adducts with C 60 and C 70 have been obtained using X-ray synchrotron radiation. Furthermore, we design a washingbased strategy to exclusively extract pure C 60 from a solid sample of cage charged with a mixture of fullerenes. These results showcase an attractive methodology to selectively extract C 60 from fullerene mixtures, providing a platform to design tuned cages for selective extraction of higher fullerenes. The solid-phase fullerene encapsulation and liberation represent a twist in host-guest chemistry for molecular nanocage structures.

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New strapped porphyrins as hosts for fullerenes: synthesis and complexation study

Cited by 20 publications

References 47 publications

Coordination chemistry on carbon surfaces

Coordination chemistry on carbon surfaces

Tautomerism and Atropisomerism in Free‐Base (meso)‐Strapped Porphyrins: Static and Dynamic Aspects

Sponge-like molecular cage for purification of fullerenes

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