Solid-state inclusion of C<sub>60</sub>and C<sub>70</sub>in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Escudero‐Adán, Eduardo C.; Bauzá, Antonio; Hernández-Eguía, Laura P.; Würthner, Frank; Ballester, Pablo; Frontera, Antonio

doi:10.1039/c6ce02341j

Cited by 15 publications

(14 citation statements)

References 63 publications

(41 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The recently introduced, somehow complementary fullerenes excel in anion‐ π catalysis because of their high polarizability and localized π holes on their surface . Anion‐ π catalysis on fullerenes is particularly attractive because the use of fullerenes in catalysis on the one hand and anion‐ π interactions on fullerenes on the other hand are both underrecognized general topics that deserve scientific attention. In fullerene anion‐ π catalyst 9 , the preorganization from the chiral cyclohexyldiamine turn was used as in NDI catalysts 4 – 6 to position a tertiary amine base close to the active fullerene surface .…”

Section: Resultsmentioning

confidence: 99%

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Zhang

Liu

López‐Andarias

et al. 2018

Helvetica Chimica Acta

View full text Add to dashboard Cite

In Memory of Gilbert StorkAnion-p interactions have been recently introduced to catalysis with the idea to stabilize anionic intermediates on p-acidic surfaces. Realized examples include enolate, enamine and iminium chemistry, domino processes and DielsAlder reactions. Moving on from the formation of contiguous stereogenic centers on p-acidic surfaces, herein we report the first asymmetric anion-p catalysis of cascade reactions that afford nonadjacent stereocenters. Conjugate addition-protonation of achiral disubstituted enolate donors to 2-chloroacrylonitrile generates 1,3-nonadjacent stereocenters with moderate enantioselectivity and diastereoselectivity. The explored catalysts operate with complementary naphthalenediimide and fullerene surfaces with highly positive quadrupole moments and high polarizability, respectively, and proximal amine bases. We find that anion-p catalysts can increase the diastereoselectivity of the reaction beyond the maximal 1:4.0 dr with conventional catalysts to maximal 5.3:1 dr on the large fullerene surfaces. The enantioselectivity of anion-p catalysts, best on the confined naphthalenediimide surfaces with strong quadrupole moment, exceed the performance of conventional catalysts except for comparable results with a new, most compact, surprisingly powerful bifunctional control catalyst. Simultaneously increased rates and stereoselectivities compared to control catalysts without p-acidic surface support that contributions of anion-p interactions to the catalytic cascade process are significant.

show abstract

Section: Resultsmentioning

confidence: 99%

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Zhang

Liu

López‐Andarias

et al. 2018

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Molecular fullerenes can be easily encapsulated into MOFs via the host-guest interaction originated from the aromatic and hydrophobic structures of them. [22,31,[39][40][41][42][43][44][45][46][47][48][49] In general, fullerenes can be encapsulated into MOFs through in-situ synthesis and post-synthesis method.…”

Section: The Encapsulation Of Fullerenes Into Mofsmentioning

confidence: 99%

“…In 2017, Escudero-Adán and co-workers [46] reported two new supramolecular assemblies (2 & 3) using adequate Zn(II)-bisporphyrin cage, perylene bisimide and fullerene through in-situ synthesis method. According to single-crystal X-ray diffraction studies, the obtained MOF compounds consist of infinite 1D polymeric chain that aggregates to form 2D sheets in two directions, which in turn pack on top of another to generate the final 3D architecture.…”

Section: The Encapsulation Of Fullerenes Into Mofsmentioning

confidence: 99%

“…The results offered inspirations to build 3D MOF by connecting metal centers of the 2D fullerene layers. [46] In 2016, Williams and co-workers [53] reported a crystalline metal-donor-fullerene framework, in which control of the donor-fullerene mutual orientation was achieved through metal coordination. The structure of fullerene-based acceptor, BPCF, was confirmed by the single-crystal X-ray Diffraction.…”

Section: The Encapsulation Of Fullerenes Into Mofsmentioning

confidence: 99%

See 1 more Smart Citation

Molecular Fullerenes Encapsulated in Metal-Organic Frameworks

Meng¹,

Wang²

2018

View full text Add to dashboard Cite

Fullerenes have many potential applications in various fields such as biomedicine, organic photovoltaics, molecular device, et al. However, it is still meaningful to explore more functional fullerene materials due to their special structures and attractive properties. In recent years, metal-organic frameworks (MOFs) have gained particular interest due to their potential applications in gas storage, catalysis, sensing, electronics, biomedicine, and so on. Considering the porous character of MOFs, it is fascinating to encapsulate molecular fullerenes into MOF pores and to construct new complex materials with unique properties and applications. In this minireview, we discuss the up-to-date study progress for the fullerene@MOF materials. We introduce firstly the preparation strategies, and then summarize the applications of these fullerene@MOF materials.

show abstract

“…[10] Consequently, numerous well-ordered nanohoop structures have been designed and synthesized as host molecules for selective encapsulation or separation of specific fullerenes. [11][12][13][14][15][16][17][18][19][20][21][22] Not long ago, Miki and coworkers [23] successfully synthesized a twin nanoring of anthracene-containing [6] cycloparaphenyleneacetylene, and studied the corresponding nanohoop-fullerene (2C 60 ) host-guest complexes, which is the first example of 1:2 complexation between a π-conjugated hydrocarbon macrocyclic system and 2 fullerene molecules. More interestingly, Wang's group [24] developed a homoditopic molecular host, janusarene, which has 2 back-to-back compactly arranged nanocavities for guest complexation.…”

Section: Introductionmentioning

confidence: 99%

Noncovalent interactions between O₆‐corona[6]arene nanorings and fullerenes C₆₀ and C₇₀: atypical ring ball‐shaped host‐guest systems

Yuan

Zhao

et al. 2018

J of Physical Organic Chem

View full text Add to dashboard Cite

The host‐guest complexes formed with quasi‐triangle‐shaped O6‐corona[3]arene[3]tetrazine (T) or O6‐corona[3]arene[3]pyridazine (P) nanorings as hosts and sphere‐like fullerene C60 or C70 as guests were investigated by density functional theory calculations with solvent effect (toluene, polarizable continuum model) being taken into account. Although the triangle‐shaped host has no geometric advantage for the fullerene recognition, the stable P@C60 (C70) and T@C70 have been experimentally detected. Therefore, on the point view of geometry features, O6‐corona[6]arenes@C60 (C70) can be regarded as a kind of atypical nano‐sized host‐guest systems. The geometry optimizations showed that fullerenes are not deeply encapsulated into the cavity of hosts O6‐corona[6]arenes but in a floating position on the cavities of hosts. The correlation between the binding energy (ΔEcp) and cavity size of the host manifests that the steric effect between host and guest is the decisive factor to determine the thermodynamic stability. The thermodynamic information indicates that the host‐guest binding processes are exothermic, enthalpy driven, and entropy opposed. Qualitative analysis based on the frontier orbital features shows that the recognition contributions brought by electron effect of charge transfer stabilization between the fullerene and the O6‐corona[6]arene nanorings can be basically excluded. Fluorescence emission spectroscopy of the free O6‐corona[6]arene molecules and their host‐guest complexes formed with fullerenes (C60 or C70) were simulated by using time‐dependent density functional theory. Additionally, the host‐guest interaction regions were detected and visualized in real space based on the electron density and reduced density gradient. Furthermore, Hirshfeld surface analysis was used for the investigation on the O6‐corona[6]arenes@C60 (C70) host‐guest interactions.

show abstract

Solid-state inclusion of C₆₀and C₇₀in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Abstract: We have conducted X-ray characterization of two unprecedented supramolecular solids involving three different components: a suitable Zn(ii)–bisporphyrin cage, a bis-pyridyl perylene derivative and a fullerene.

Cited by 15 publications

References 63 publications

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Molecular Fullerenes Encapsulated in Metal-Organic Frameworks

Noncovalent interactions between O₆‐corona[6]arene nanorings and fullerenes C₆₀ and C₇₀: atypical ring ball‐shaped host‐guest systems

Contact Info

Product

Resources

About

Solid-state inclusion of C60and C70in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Abstract: We have conducted X-ray characterization of two unprecedented supramolecular solids involving three different components: a suitable Zn(ii)–bisporphyrin cage, a bis-pyridyl perylene derivative and a fullerene.

Cited by 15 publications

References 63 publications

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Molecular Fullerenes Encapsulated in Metal-Organic Frameworks

Noncovalent interactions between O6‐corona[6]arene nanorings and fullerenes C60 and C70: atypical ring ball‐shaped host‐guest systems

Contact Info

Product

Resources

About

Solid-state inclusion of C₆₀and C₇₀in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Noncovalent interactions between O₆‐corona[6]arene nanorings and fullerenes C₆₀ and C₇₀: atypical ring ball‐shaped host‐guest systems