Concise Route to Symmetric Multiadducts of [60]Fullerene:  Preparation of an Equatorial Tetraadduct by Orthogonal Transposition

Schwenninger, Reinhold; Müller, Thomas; Kräutler, Bernhard

doi:10.1021/ja971875p

“…Reaction of symmetric C 60 tetrakis-adduct 8 [23] with paraformaldehyde and terpyridylglycine in refluxing 1,2-dichlorobenzene afforded both bis-and mono(terpyridyl) C 60 adducts 2 and 9, respectively. It is interesting to observe that mono(terpyridyl) compound 9 was always present even after increasing the reaction time and/or by using a large excess of paraformaldehyde and terpyridylgylcine.…”

Section: Synthesis Of 2 Andmentioning

confidence: 99%

“…[23] Gold wire (99.999 %) was obtained commercially. NMR spectra were recorded on a Bruker Ac 300 or 500 spectrometer.…”

Section: Full Papermentioning

confidence: 99%

“…[22] By reacting 6 with an excess of diethylbromomalonate, Kräutler et al obtained the D 2h -symmetric hexakis-adduct 7 in 95 % yield (Scheme 4). [23] Due to the thermal instability of the anthracene addends, a C 60 tetrakis-adduct 8 with all addends located on an equatorial belt was obtained in 88 % yield. Our synthetic strategy is based on this easily prepared tetrakis-adduct of C 60 (8), shown in Schemes 5 and 6 (see below).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Fullerene Adducts with Terpyridyl‐ or Pyridylpyrrolidine Groups in trans‐1 Positions

Zhang

¹

,

Lukoyanova

²

,

Echegoyen

³

2006

Chemistry A European J

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Two C(60) hexakis-adducts (2 and 3) were synthesized by using a protection-deprotection strategy. The symmetric fullerene tetrakis-adduct 8 was obtained by anthracene removal from the hexakis-adduct 7. Reaction of 8 with terpyridylglycine or pyridylglycine afforded two hexakis-adducts, 2 and 3. By using the retro-cyclopropanation reaction, the four malonate addends located on the equatorial belt of the hexakis-adducts were removed to afford two trans-1 bis-adducts, 4 and 5, with terpyridyl- or pyridylpyrrolidine groups. The structures of 2 and 3 were confirmed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and (1)H, (13)C, and COSY NMR, and UV-visible spectroscopy. The cyclic voltammograms of fullerene multiadducts 2, 3, and 9 show irreversible reductions. Self-assembled monolayers (SAMs) of 1 and 3 were formed on gold surfaces through nitrogen adsorption. SAMs of 3 represent the first example of a fullerene hexakis-adduct formed on gold surfaces through nitrogen adsorption. Controlled potential electrolyses (CPE) were conducted to prepare trans-1 bis-adducts 4 and 5 modified with terpyridyl and pyridyl groups.

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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%

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...

show abstract

“…[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%

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...

show abstract

Concise Route to Symmetric Multiadducts of [60]Fullerene: Preparation of an Equatorial Tetraadduct by Orthogonal Transposition

Cited by 87 publications

References 21 publications

Synthesis of Fullerene Adducts with Terpyridyl‐ or Pyridylpyrrolidine Groups in trans‐1 Positions

Synthesis of Fullerene Adducts with Terpyridyl‐ or Pyridylpyrrolidine Groups in trans‐1 Positions

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

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