Regioselective Synthesis of 1,4-Di(organo)[60]fullerenes through DMF-assisted Monoaddition of Silylmethyl Grignard Reagents and Subsequent Alkylation Reaction

Matsuo, Yutaka; Iwashita, Akihiko; Abe, Yohei; Li, Chang‐Zhi; Matsuo, Kazuya; Hashiguchi, Masaaki; Nakamura, Eiichi

doi:10.1021/ja8041299

Cited by 155 publications

(92 citation statements)

References 61 publications

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“…In comparison with the 58³-electron-conjugated system in the case of 1,2-addition, the system in the case of 1,4-addition exhibits a higher LUMO level and lower electron affinity. 14,15 For this reason higher opencircuit voltage is obtained from 1,4-diadducts of fullerene. 1618 1,4-Bis(silylmethyl)fullerene, which has a 58³-electronconjugated system, is synthesized as follows.…”

Section: ç Improvement Of Open-circuit Voltage By Installation Of Elementioning

confidence: 99%

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Design Concept for High-LUMO-level Fullerene Electron-acceptors for Organic Solar Cells

Matsuo

2012

Chemistry Letters

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112

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This review article describes design concept, synthesis, and features of fullerene derivatives having high lowest unoccupied molecular orbital (LUMO) levels to achieve high open-circuit voltage in organic thin-film photovoltaic devices. Installation of organic electron-donating groups onto fullerene and decrease of the size of the fullerene ³-electron-conjugated system raise the LUMO levels, affording high-performance organic solar cells. Addition of the methano group as the smallest carbon addend to fullerene to obtain 56³-electron fullerene derivatives is likely a promising strategy for this purpose. Ç IntroductionOrganic thin-film solar cells are lightweight and flexible, and thus are expected to allow for low-cost production through a printing process. 1 The active layer that converts light into electricity contains organic semiconductors, whose development is the key to improving power conversion efficiency. Accordingly, organic chemistry has a major role to play. Up to now, the development of organic thin-film solar cells has been led by material scientists and device engineers, but there is increasing demand for collaboration with synthetic chemists who can design and synthesize organic semiconductor molecules.Although the power conversion efficiency of organic thinfilm solar cells was about 1% before 2000, a sharp increase in conversion efficiency was seen after 2000, owing to the discovery of the combination of poly(3-hexylthiophene) (P3HT; an organic electron-donor) and phenyl-C 61 -butyric acid methyl ester (PCBM; an organic electron-acceptor).2 When heated and exposed to solvent vapor, P3HT undergoes self-assembly and forms ³-stacked structures, improving its electrical properties and light absorption characteristics. Furthermore, PCBM is a fullerene derivative that is soluble in organic solvents, and its solubility allows for blend solutions containing P3HT to be prepared over a range of concentrations. Furthermore, thin films prepared through the use of a P3HT/PCBM blend solution have made it possible to develop composite films with a bulk heterojunction structure, in which an electron-donor and an electron-acceptor are suitably mixed.3 In comparison with conventional pn heterojunction devices, bulk heterojunction devices have a greater interface area between the donor and acceptor and charge separation is more efficient. In this way, around 2005, power conversion efficiency reached 45%. 4 In the last few years, the power conversion efficiency of organic thin-film solar cells has increased further to about 10%. 5This vast improvement was largely due to the development of new materials, for example, new electron-donors such as low band gap polymers, 6 which are capable of absorbing longwavelength light. These materials are alternating copolymers with electron-rich and electron-deficient parts, and for this reason they have high-lying HOMO and low-lying LUMO levels. Intermolecular charge transfer from electron-rich parts to electron-deficient parts makes such materials capable of absorbing...

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Section: ç Improvement Of Open-circuit Voltage By Installation Of Elementioning

confidence: 99%

“…Indene C 60 bisadduct (ICBA,14) 2830 is obtained by addition of isoindene to C 60 , where isoindene is obtained by isomerization of indene at 214°C in 1,2,4-trichlorobenzene and other solvents with a high boiling point. Along with ICBA, this reaction also yields indene mono-, tri-, and polyadducts.…”

Section: 24mentioning

confidence: 99%

Design Concept for High-LUMO-level Fullerene Electron-acceptors for Organic Solar Cells

Matsuo

2012

Chemistry Letters

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112

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“…Covalent approaches include radical-driven additions, 14,15 the Bingel-Hirsch cyclopropanation reaction, 16,17 and azomethine ylide-driven 1,3-cycloadditions, [18][19][20] among others, such as carboxylation and Grignard reactions. [21][22][23] The regiochemistry of the applicable reactions favors addition across [6,6] over [6,5] carbon-carbon bonds found on SWCNT caps and spherical fullerenes; calculations have shown that adducts to the [6,6] carbons are more thermodynamically stable, driven in part by the bond's more conducive π-orbital and alkene-like character. 24,25 Identical reaction mechanisms and products on C60 buckminsterfullerene (or "buckyballs"), a discrete and homogeneous allotrope of carbon, served as a platform in this work, to aid in the structural elucidation of SWCNT adducts that are resistant to standard spectroscopy methods.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, pharmacokinetics, and biological use of lysine-modified single-walled carbon nanotubes

Feinberg¹,

Alidori²,

McDevitt³

et al. 2014

IJN

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We aimed to create a more robust and more accessible standard for amine-modifying single-walled carbon nanotubes (SWCNTs). A 1,3-cycloaddition was developed using an azomethine ylide, generated by reacting paraformaldehyde and a side-chain-Boc (tert-Butyloxycarbonyl)-protected, lysine-derived alpha-amino acid, H-Lys(Boc)-OH, with purified SWCNT or C60. This cycloaddition and its lysine adduct provides the benefits of dense, covalent modification, ease of purification, commercial availability of reagents, and pH-dependent solubility of the product. Subsequently, SWCNTs functionalized with lysine amine handles were covalently conjugated to a radiometalated chelator, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA). The 111 In-labeled construct showed rapid renal clearance in a murine model and a favorable biodistribution, permitting utility in biomedical applications. Functionalized SWCNTs strongly wrapped small interfering RNA (siRNA). In the first disclosed deployment of thermophoresis with carbon nanotubes, the lysine-modified tubes showed a desirable, weak SWCNT-albumin binding constant. Thus, lysine-modified nanotubes are a favorable candidate for medicinal work.

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“…In contrast, non-conventional mesogens, which have become very popular in recent years, lack such shape-anisotropy of the core unit. Among them, are bent-core mesogens, multi-arm mesogens, cones (Xu and Swager 1993;Komori and Shinkai 1993) shuttle-cocks (Sawamura et al 2002;Matsuo et al 2004), dendrons, dendrimers (Percec et al 2002;Saez et al 2001;Baars et al 1998) supramolecular mesogens, such as metallomesogens (Cardinaels et al 2005) and hydrogen-bonded mesogens (Paleos and Tsiourvas 2001;Saez and Goodby 2005), rod-dendrons (Lecommandoux et al 2003) and rings (Mindyuk et al 1998), have gained significant recognitions.…”

Section: Non-conventional Shaped Liquid Crystalsmentioning

confidence: 99%

Side Chain Liquid Crystalline Polymers: Advances and Applications

Reddy

Jayaramudu

Ray

et al. 2015

Liquid Crystalline Polymers

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Matters comprise of molecules that exist in three different phases-solids, liquids and gases depending on their arrangement. The arrangement of molecules in a crystalline solid leads to long-range positional and orientational orders. In isotropic liquid, on the other hand, the molecules are arranged randomly and possess no order and flow freely. However, it was observed that a certain class of molecules organise in a different manner in order to exhibit a new phase, popularly known as liquid crystalline phase. Molecules in liquid crystalline phase self-organize, leading to positional/orientation order. Macroscopically, the liquid crystalline phase exhibits flow and appears like an opaque fluid.

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Regioselective Synthesis of 1,4-Di(organo)[60]fullerenes through DMF-assisted Monoaddition of Silylmethyl Grignard Reagents and Subsequent Alkylation Reaction

Cited by 155 publications

References 61 publications

Design Concept for High-LUMO-level Fullerene Electron-acceptors for Organic Solar Cells

Design Concept for High-LUMO-level Fullerene Electron-acceptors for Organic Solar Cells

Synthesis, pharmacokinetics, and biological use of lysine-modified single-walled carbon nanotubes

Side Chain Liquid Crystalline Polymers: Advances and Applications

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