Design, Synthesis, and X‐Ray Crystal Structure of a Fullerene‐Linked Metal–Organic Framework

Peng, Ping; Li, Fangfang; Neti, Venkata S. Pavan K.; Metta‐Magaña, Alejandro J.; Echegoyen, Luís

doi:10.1002/anie.201306761

“…[3] There are few known reports of spatial organization of graphitic crystalline materials through the covalent linkage of fullerene derivatives. [4][5][6][7][8] Moreover,the known approaches for fulleretic material organization are mainly based on immobilization of the fullerenes inside porous matrices possessing alarge aperture. [9][10][11] There are very few reports of crystalline fullerene-metal-coordinated extended structures.…”

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confidence: 99%

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Williams

¹

,

Dolgopolova

²

,

Godfrey

³

et al. 2016

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Herein, we report the first example of ac rystalline metal-donor-fullerene framework, in which control of the donor-fullerene mutual orientation was achieved through chemical bond formation, in particular,bymetal coordination. The 13 Cc ross-polarization magic-angle spinning NMR spectroscopy, X-rayd iffraction, and time-resolved fluorescence spectroscopyw ere performed for comprehensive structural analysis and energy-transfer (ET) studies of the fulleretic donor-acceptor scaffold. Furthermore,i nc ombination with photoluminescence measurements,t he theoretical calculations of the spectral overlap function, Fçrster radius,e xcitation energies,a nd band structure were employed to elucidate the photophysical and ET processes in the prepared fulleretic material. We envision that the well-defined fulleretic donoracceptor materials could contribute not only to the basic science of fullerene chemistry but would also be used towards effective development of organic photovoltaics and molecular electronics.The success of fullerenes and their derivatives in engineering organic photovoltaics and molecular electronics is mainly owed to their electron-accepting properties and ultrafast electron/energy transfer. [1,2] As previously demonstrated, fullerene(acceptor)-donor alignment could significantly affect excitonic device performance.F or instance,t he arrangement of the donor fullerene is crucial for efficient energy/charge transfer, because of possible effects on the distance of exciton diffusion, p-p stacking, or Fçrster radius (resonance energy transfer). As ar esult, formation of fullerene stacks led to an enhancement of solar cell efficiency,in contrast to non-stacking fullerene derivatives. [3] There are few known reports of spatial organization of graphitic crystalline materials through the covalent linkage of fullerene derivatives. [4][5][6][7][8] Moreover,the known approaches for fulleretic material organization are mainly based on immobilization of the fullerenes inside porous matrices possessing alarge aperture. [9][10][11] There are very few reports of crystalline fullerene-metal-coordinated extended structures. [12][13][14][15] Furthermore,n one of these studies explore the concept demonstrated herein, which tackles the development of an ovel crystalline metal-donor-acceptor framework, in which control of the mutual orientation of the donor and fullerenebased acceptor was achieved through chemical bond formation, that is,m etal coordination. Despite the tremendous interest in self-assemblies (in particular,c oordination polymers such as covalent or metal-organic frameworks;COFs or MOFs) [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and fullerene chemistry,t ot he best of our knowledge the prepared metal-organic fullerene-containing framework is the first example of ac rystalline hybridextended structure,inw hich control over mutual orientation of both donor and fullerene-based acceptor is achieved through metal coordination (Scheme 1). Scheme 1. As chematic representation of organizatio...

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“…[3] There are few known reports of spatial organization of graphitic crystalline materials through the covalent linkage of fullerene derivatives. [4][5][6][7][8] Moreover,the known approaches for fulleretic material organization are mainly based on immobilization of the fullerenes inside porous matrices possessing alarge aperture. [9][10][11] There are very few reports of crystalline fullerene-metal-coordinated extended structures.…”

mentioning

confidence: 99%

“…As previously shown, reactions of tetrakis(4-carboxyphenyl)porphyrin (H 4 TCPP) linkers with metal salts (in the absence of BPCF) led to the formation of two-dimensional planar Zn 2 (ZnTCPP) layers,i nw hich the porphyrin-containing donors were connected through Zn 2 (O 2 C-) secondary building units (SBUs). [37] Figure S3 shows that the solvent molecules occupy the apical positions of the Zn 2 (O 2 C-) 4 SBUsand could be replaced by different linkers which connect two adjacent Zn 2 (ZnTCPP) layers ( Figure S4). Thus,Zn 2+ ions in Zn 2 (O 2 C-) 4 could be used as anchor points for arrangement of the fullerene-based acceptors by coordinative immobilization between the layers.T op repare such af ullerene-porphyrin crystalline hybrid framework, H 4 TCPP and BPCF were heated in the presence of zinc nitrate at 80 8 8Cf or 16 h, which resulted in formation of [Zn 2 (ZnTCPP)(BPCF) 0.23 -(DEF) 0.77 ]·2(EtOH)·0.2H 2 O( 1, Scheme 1; the synthetic details can be found in the Supporting Information).…”

mentioning

confidence: 99%

“…[37] Figure S3 shows that the solvent molecules occupy the apical positions of the Zn 2 (O 2 C-) 4 SBUsand could be replaced by different linkers which connect two adjacent Zn 2 (ZnTCPP) layers ( Figure S4). Thus,Zn 2+ ions in Zn 2 (O 2 C-) 4 could be used as anchor points for arrangement of the fullerene-based acceptors by coordinative immobilization between the layers.T op repare such af ullerene-porphyrin crystalline hybrid framework, H 4 TCPP and BPCF were heated in the presence of zinc nitrate at 80 8 8Cf or 16 h, which resulted in formation of [Zn 2 (ZnTCPP)(BPCF) 0.23 -(DEF) 0.77 ]·2(EtOH)·0.2H 2 O( 1, Scheme 1; the synthetic details can be found in the Supporting Information). Interestingly,e mployment of the same synthetic scheme for incorporation of the parent fullerene C 60 (i.e., without pyridyl groups) within porphyrin layers was not successful.…”

mentioning

confidence: 99%

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Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Williams

¹

,

Dolgopolova

²

,

Godfrey

³

et al. 2016

View full text Add to dashboard Cite

Herein, we report the first example of ac rystalline metal-donor-fullerene framework, in which control of the donor-fullerene mutual orientation was achieved through chemical bond formation, in particular,bymetal coordination. The 13 Cc ross-polarization magic-angle spinning NMR spectroscopy, X-rayd iffraction, and time-resolved fluorescence spectroscopyw ere performed for comprehensive structural analysis and energy-transfer (ET) studies of the fulleretic donor-acceptor scaffold. Furthermore,i nc ombination with photoluminescence measurements,t he theoretical calculations of the spectral overlap function, Fçrster radius,e xcitation energies,a nd band structure were employed to elucidate the photophysical and ET processes in the prepared fulleretic material. We envision that the well-defined fulleretic donoracceptor materials could contribute not only to the basic science of fullerene chemistry but would also be used towards effective development of organic photovoltaics and molecular electronics.The success of fullerenes and their derivatives in engineering organic photovoltaics and molecular electronics is mainly owed to their electron-accepting properties and ultrafast electron/energy transfer. [1,2] As previously demonstrated, fullerene(acceptor)-donor alignment could significantly affect excitonic device performance.F or instance,t he arrangement of the donor fullerene is crucial for efficient energy/charge transfer, because of possible effects on the distance of exciton diffusion, p-p stacking, or Fçrster radius (resonance energy transfer). As ar esult, formation of fullerene stacks led to an enhancement of solar cell efficiency,in contrast to non-stacking fullerene derivatives. [3] There are few known reports of spatial organization of graphitic crystalline materials through the covalent linkage of fullerene derivatives. [4][5][6][7][8] Moreover,the known approaches for fulleretic material organization are mainly based on immobilization of the fullerenes inside porous matrices possessing alarge aperture. [9][10][11] There are very few reports of crystalline fullerene-metal-coordinated extended structures. [12][13][14][15] Furthermore,n one of these studies explore the concept demonstrated herein, which tackles the development of an ovel crystalline metal-donor-acceptor framework, in which control of the mutual orientation of the donor and fullerenebased acceptor was achieved through chemical bond formation, that is,m etal coordination. Despite the tremendous interest in self-assemblies (in particular,c oordination polymers such as covalent or metal-organic frameworks;COFs or MOFs) [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and fullerene chemistry,t ot he best of our knowledge the prepared metal-organic fullerene-containing framework is the first example of ac rystalline hybridextended structure,inw hich control over mutual orientation of both donor and fullerene-based acceptor is achieved through metal coordination (Scheme 1). Scheme 1. As chematic representation of organizatio...

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“…[9] An alternative approach with metal-coordinated connections in between the fullerene derivatives produced 2D-layered structures with very small pores. [10] Despite the synthetic efforts in the field of fullerene polymers and other fullerene-based materials,t oo ur knowledge no examples exist of covalently crosslinked fullerene materials with three-dimensional order and stable high porosity.T he introduction of ordered porosity is expected to create additional desirable features,such as high surface area and molecular discrimination, that would be beneficial for catalytic applications or electronic interactions of the fullerene pore-wall material with molecular guests. [11] Herein we demonstrate the first example of as table covalent fullerene framework exhibiting ahighly-periodic 3D pore system with around 7.5 nm pore diameter.T his high porosity was achieved by developing an evaporation-induced self-assembly (EISA) strategy of af ullerene precursor templated by al iquid-crystalline block copolymer inducing high periodicity and porosity.I nt his context, fullerene molecules can be modified at many points on their surface, potentially resulting in am ultitude of adducts with different symmetries and av arying number of functionalities.T his would lead to ac omplicated coassembly behavior between the precursor and template,and likely produce limited order in the final product.…”

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confidence: 99%

A Highly‐Ordered 3D Covalent Fullerene Framework

Minar

¹

,

Hou

²

,

Westermeier

³

et al. 2015

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Ah ighly-ordered 3D covalent fullerene framework is presented with as tructure based on octahedrally functionalized fullerene building blocks in whiche very fullerene is separated from the next by six functional groups and whose mesoporosity is controlled by cooperative self-assembly with aliquid-crystalline blockcopolymer.The new fullerene-framework material was obtained in the form of supported films by spin coating the synthesis solution directly on glass or silicon substrates,followed by aheat treatment. The fullerene building blocks coassemble with aliquid-crystalline blockcopolymer to produce ah ighly ordered covalent fullerene framework with orthorhombic Fmmm symmetry,a ccessible 7.5 nm pores,a nd high surface area, as revealed by gas adsorption, NMR spectroscopy, small-angle X-rays cattering (SAXS), and TEM. We also note that the 3D covalent fullerene framework exhibits adielectric constant significantly lower than that of the nonporous precursor material.

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Design, Synthesis, and X‐Ray Crystal Structure of a Fullerene‐Linked Metal–Organic Framework

Cited by 57 publications

References 30 publications

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

A Highly‐Ordered 3D Covalent Fullerene Framework

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