Hydroxide-Initiated Conversion of Aromatic Nitriles to Imidazolines: Fullerenes vs TCNE

Hou, Hui‐Lei; Li, Zongjun; Li, Shu-Hui; Chen, Si; Gao, Xiang

doi:10.1021/ol401834j

Cited by 16 publications

(23 citation statements)

References 37 publications

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“…Based on this, as well as the large mismatch in standard reduction potentials between OH À /F À and C 60 , 14 we hypothesized that the reported observation of radical species resulted from an initial chemical reaction between the nucleophile and C 60 followed by electron transfer to a second C 60 molecule (Scheme 1). Similar reactions have been demonstrated previously in both solution and the solid state [15][16][17][18] Such reaction chemistry would result in the generation of numerous potential products. The understanding of such chemistry is essential for elucidation of a mechanistic description of interface energetics and charge extraction processes towards the rational design of highly efficient OPVs.…”

supporting

confidence: 69%

“…Oxidations of this type have been observed by numerous groups and have been utilized in the synthesis of various fullerene derivatives. 15,17 The observation of fast electron transfer kinetics in step II is supported by studies of selfexchange rate constants for fullerene adduct anions (1.9 Â 10 8 M À1 s À1 ). 29 However, 19 F NMR analysis of deoxygenated reaction solutions did not indicate the presence of C-F bonding.…”

mentioning

confidence: 88%

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Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride

2014

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The solution phase n-doping of C 60 and PCBM with tetrabutylammonium fluoride is shown to occur via an initial chemical reaction followed by electron transfer to a second fullerene molecule. The formation of ionic and radical intermediate species has significant implications for the use of ionically functionalized materials as electron-selective interface layers in OPVs.The use of ionically functionalized polymers and molecules as electron-selective interfacial layers in organic photovoltaic cells (OPVs) has attracted signicant research interest in recent years. 1-5 Devices fabricated using these materials, such as ionically functionalized polyuorenes and fullerenes, have displayed power conversion efficiencies up to $9%, largely due to an increase in the cell open-circuit voltage (V oc ). 1-5 Despite these advances, the mechanism by which these materials affect device performance remains uncertain. 1-8 The observed increase in V oc is typically attributed to electrode work function reduction from preferential orientation of ionic pendant groups and associated counterions, resulting in a net dipole. 1-7 While it is likely that interfacial dipoles are present, the role of potential chemical reactions between the ionically functionalized material and active layer has received relatively little attention. 7,9,10 Recently, Li et al. reported unusually high conductivities (up to 3.2 S m À1 ) in PCBM/fulleropyrrolidinium iodide blend thin lms. 11 It was shown subsequently that lms deposited from solutions of tetrabutylammonium salts (TBAX: X ¼ F, Br, I, OH, AcO) and PCBM also resulted in highly conducting lms. 12 Based on solution phase studies using C 60 , it was postulated that direct electron transfer from anion (OH À or F À ) to fullerene results in the n-doped C 60 radical anion (C 60 _ À ) and donor radical (OH_ or F_). These studies suggest that redox reactions between the interfacial material anions and PCBM in the active layer results in interfacial n-doping which would have signi-cant effects on interfacial energetics and charge extraction. However, given the electrophilicity of the fullerene molecule and nucleophilicity of anions studied, particularly F À and OH À , 13 the possibility of chemical reactions is signicant in both solution and solid state. Based on this, as well as the large mismatch in standard reduction potentials between OH À /F À and C 60 , 14 we hypothesized that the reported observation of radical species resulted from an initial chemical reaction between the nucleophile and C 60 followed by electron transfer to a second C 60 molecule (Scheme 1). Similar reactions have been demonstrated previously in both solution and the solid state 15-18 Such reaction chemistry would result in the generation of numerous potential products. The understanding of such chemistry is essential for elucidation of a mechanistic description of interface energetics and charge extraction processes towards the rational design of highly efficient OPVs.UV-vis-NIR spectroscopy was used to monitor the reaction be...

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supporting

confidence: 69%

mentioning

confidence: 88%

Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride

2014

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“…In 2013, Gao and co-workers reported the conversion of aromatic nitriles (337) to 2-imidazolines (339) with the electron-deficient C 60 or C 70 fullerenes (338) (Scheme 95). [93] The reaction optimization and substrates scope were performed by using aromatic nitriles (337) and fullerene (338) under the basic condition of TBAOH (tetra-n-butylammonium hydroxide, 1.0 M in MeOH) at different temperatures. At 90°C, the fullerene fused imidazolines were isolated in moderate yields (36-43%).…”

Section: Methods F: Synthesis Of Imidazolines From Cyanidesmentioning

confidence: 99%

Recent Advances in the Synthesis of Imidazolines (2009–2020)

Mehedi

Tepe

2020

Adv Synth Catal

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Imidazoline is an important class of compounds found in numerous natural and pharmaceutical products. The compounds are also used as an intermediate in the synthesis of organic molecules. Moreover, chiral imidazolines are widely utilized as organocatalysts to synthesize various natural and synthetic organic compounds. In the past decade, there was an increase in interest in developing new methods to synthesize these imidazoline analogs. Both modification of the previously established methods and the development of new methods are carried out significantly. This review article highlights the progress of the synthesis of imidazoline scaffolds in the last few years (2009-present). The review also described the proposed mechanism illustrated in many of the reports.

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“…3 a) via solution-mediated cyclotrimerization. However, the solution-mediated cyclotrimerization only led to the formation of a dimer product 3 34 , which is confirmed by NMR, mass spectra and XRD (Supplementary Figs. 6 – 8 ).…”

Section: Resultsmentioning

confidence: 56%

On-surface synthesis of triangulene trimers via dehydration reaction

Cheng

Xue

et al. 2022

Nat Commun

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Triangulene and its homologues are of considerable interest for molecular spintronics due to their high-spin ground states as well as the potential for constructing high spin frameworks. Realizing triangulene-based high-spin system on surface is challenging but of particular importance for understanding π-electron magnetism. Here, we report two approaches to generate triangulene trimers on Au(111) by using surface-assisted dehydration and alkyne trimerization, respectively. We find that the developed dehydration reaction shows much higher chemoselectivity thus resulting in significant promotion of product yield compared to that using alkyne trimerization approach, through cutting the side reaction path. Combined with spin-polarized density functional theory calculations, scanning tunneling spectroscopy measurements identify the septuple (S = 3) high-spin ground state and quantify the collective ferromagnetic interaction among three triangulene units. Our results demonstrate the approaches to fabricate high-quality triangulene-based high spin systems and understand their magnetic interactions, which are essential for realizing carbon-based spintronic devices.

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Hydroxide-Initiated Conversion of Aromatic Nitriles to Imidazolines: Fullerenes vs TCNE

Cited by 16 publications

References 37 publications

Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride

Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride

Recent Advances in the Synthesis of Imidazolines (2009–2020)

On-surface synthesis of triangulene trimers via dehydration reaction

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Hydroxide-Initiated Conversion of Aromatic Nitriles to Imidazolines: Fullerenes vs TCNE

Cited by 16 publications

References 37 publications

Solution phase n-doping of C60and PCBM using tetrabutylammonium fluoride

Solution phase n-doping of C60and PCBM using tetrabutylammonium fluoride

Recent Advances in the Synthesis of Imidazolines (2009–2020)

On-surface synthesis of triangulene trimers via dehydration reaction

Contact Info

Product

Resources

About

Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride

Solution phase n-doping of C₆₀and PCBM using tetrabutylammonium fluoride