Synthesis and Crystal Structure of a [70]Fullerene–Pentacene Monoadduct

Shirai, Hitoshi; Tajima, Tomoyuki; Kubo, Kazuyuki; Nishihama, Takuya; Miyake, Hideaki; Takaguchi, Yutaka

doi:10.1246/bcsj.20150378

Cited by 5 publications

(2 citation statements)

References 34 publications

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“…The single‐crystal X‐ray diffraction analysis of 2 a confirmed that the dihydropentacene moiety is attached to the fullerene at the 6‐ and 13‐position, which results in C 2v symmetry (Figure ). Furthermore, it revealed a nested crystal packing, i. e., each [60]fullerene moiety nests within the pentacene arms of an adjacent molecule of 2 a via π‐π interactions, which has previously been reported by Miller and co‐workers and by our group . The intermolecular close‐contact distance between the fullerene and the naphthalene moiety of the pentacene arms is ∼3.5 Å, and this intermolecular attractive interaction should assist the self‐assembly of 2 a and 2 b in solution.…”

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confidence: 69%

Self‐Assembly and Fluorescence Properties of [60]Fullerene‐Pentacene Monoadducts

et al. 2017

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The highly soluble [60]fullerene-pentacene monoadducts 2 a and 2 b were synthesized by a Diels-Alder reaction between [60]fullerene and pentacene derivatives. The single-crystal X-ray diffraction analysis of 2 a revealed an attractive intermolecular interaction between [60]fullerene moiety of one molecule and the pentacene arms of an adjacent molecule, resulting in the formation of head-to-tail dimers in solution. This self-association behavior of 2 a and 2 b was also observed by 1 H NMR and fluorescence spectroscopy in chloroform. Both the excitation and emission wavelengths can be modulated via the concentration of 2 a and 2 b.Fluorescent materials that respond to external stimuli [1][2][3][4] are of great interest, both from a fundamental materials science perspective and with respect to practical applications in sensors, [5,6] security papers, [7,8] optoelectronic switches, [9,10] and information-storage devices. [11,12] Especially methods to control the self-assembly structures of such materials in the solid state or in solution have attracted much attention, due to the potential utility in switchable dual-emission materials. [13][14][15][16][17][18][19][20][21][22][23][24][25][26] However, examples for molecules that are capable of switching the wavelength of not only the emission but also the excitation by changing their self-assembled structures remain scarce. [27,28] Fullerene-pentacene monoadducts represent in this context highly promising prospectives, as they exhibit switchable dual emission and dual excitation on account of the presence of two fluorophores (fullerene and naphthalene moieties) and their nested crystal packing, i. e., each fullerene moiety nests within the pentacene arms of an adjacent monoadduct via p-p interactions. [29][30][31][32] However, studies on the self-association and fluorescence behavior of fullerene-pentacene monoadducts in solution have not yet been reported, most likely due to a lack of soluble derivatives. We were therefore interested in preparing highly soluble fullerene-pentacene monoadducts. Herein, we describe the self-assembly and fluorescence properties of [60]fullerene-pentacene monoadducts in solution.Highly soluble [60]fullerene-pentacene monoadducts 2 a and 2 b were synthesized by Diels-Alder reactions between [60] fullerene and the previously reported pentacene derivatives 1 a and 1 b, [33] respectively (Scheme 1). A solution of 1 a and [60] fullerene in o-dichlorobenzene was stirred for 20 h at 45 8C under an atmosphere of argon in the dark. After purification by column chromatography on silica gel (eluent: CHCl 3 ) and GPLC (CHCl 3 ), brown crystals of 2 a were obtained in 89 % yield. A similar reaction using 1 b instead of 1 a afforded 2 b in 75 % yield. As expected, 2 a and 2 b are highly soluble in various organic solvents including toluene, benzene, benzonitrile, THF, chloroform, and dichloromethane. Moreover, 2 a and 2 b are stable in the dark and can be kept for several months at room temperature, i. e., retro-Diels-Alder reactions of 2 a and 2 b ...

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Section: Figuresupporting

confidence: 69%

Self‐Assembly and Fluorescence Properties of [60]Fullerene‐Pentacene Monoadducts

et al. 2017

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“…Consequently, several interesting results have been observed such as a temperature-dependent interface morphologies [19], hetero-epitaxial growth at the interface [20,21], and orientation-dependent efficiences of photovoltaic cells [22]. Interestingly, however, one important and potentially challenging aspect of this 'ideal model system' is frequently not considered: it is well-known that acenes and fullerenes can undergo a [4+2] Diels-Alder (D-A) cycloaddition reaction in solution under formation of molecular adducts [23][24][25][26][27][28][29][30][31][32]. As in other D-A reactions of acenes [33,34] these act as electron-rich dienes while the fullerene is the dienophile.…”

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confidence: 99%

Diels–Alder adduct formation at solid interfaces between fullerenes and acenes

Breuer¹,

Geiger²,

Bettinger³

et al. 2018

J. Phys.: Condens. Matter

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Understanding organic-organic interfaces is rather challenging due to their large complexity regarding morphology, molecular orientation at the interface, interdiffusion, and energetics. One additional important but often neglected aspect are chemical reactions occuring at such interfaces. For solid interfaces between pentacene and Buckminster-Fullerene (C 60 ) recently very efficient Diels-Alder (D-A) adduct formation has been reported. Considering the importance of pentacene/C 60 as prototypical donor-acceptor combination to study fundamental processes in organic photovoltaics, understanding this effect is essential. In this work, we provide detailed NEXAFS-based investigations with respect to the temperature-dependence and reaction zone depth of this effect. Moreover, we widely vary the interface morphology and observe that the D-A adduct formation is most efficient for bulk heterojunctions of pentacene and C 60 . By also investigating further material combinations such as PEN/C 60 -PCBM and interfaces between C 60 and functionalized acenes, we observe trends for the occurrence of the D-A adduct formation correlated with the different chemical properties of the involved compounds.

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