Synthesis and characterization of C60 and C70 acetylace-tone monoadducts and study of their photochemical properties for potential application in solar cells / Síntesis y caracterización de monoaductos de C60 y C70 con acetilacetona y estudio de sus propiedades fotoquímicas para su posible aplicación en células solares / Sínteses e caracterização de monoadutos de C60 e C70 com acetilacetona e estudo das suas propriedades fotoquímicas para a sua possível aplicação em células solares

Abstract We report on the synthesis of C60 and C70 monoadducts at room temperature through the Bingel reaction; employing acetylacetone as ligand; in presence of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), carbon tetrabromide (CBr4), and o-dichlorobenzene. Diacetylmethane-[C60-Ih]-fullerene-[5,6] and diacetylmethane-[C70-D5h]-fullerene-[5,6] monoadducts were obtained with yields of 69% and 44%, respectively. The products were purified by column chromatography (CC, on silica gel, using hexane, carbon disulfide, and chloroform as eluents at room temperature) and characterized by Nuclear Magnetic Resonance ('H and 13C), Fourier-Transform Infrared (FT-IR) and UV-Visible spectroscopies, Matrix-assisted Laser Desorption/Ionization-Time of Flight (MALDI-TOF) Mass spectrometry, Cyclic Voltammetry (CV), and Osteryoung Square Wave Voltammetry (OSWV). Both compounds showed irreversible reduction peaks controlled by diffusion, with LUMO energy levels of -3.09 eV, -3.13 eV for C60, and C70 monoadducts, respectively. These values are comparable with the -3.99 eV of PC61BM. The synthetized adducts were incorporated into inverted-type perovskite solar cells and were used as electron transporting materials (ETM) obtaining power conversion efficiencies (PCE) of 8.5% and 14.0% for the C60 and C70 monoadducts, respectively. When C60 is replaced by a lower symmetrical fullerene such as C70 an improved light absorption in the visible region is observed.

Resumen Reportamos la síntesis de monoadductos de C60 y C70 a temperatura ambiente a través de la reacción de Bingel, empleando acetilacetona como ligando, en presencia de DBU (1,8-diazabiciclo [5.4.0] undec-7-eno), tetrabromuro de carbono (CBr4) y o-diclorobenceno. Se obtuvieron monoadductos de diacetilmetano-[C -I.]-fullereno-[5,6] y diacetilmetano-[C70-D5h]-fullereno-[5,6] con rendimientos del 69% y 44%, respectivamente. Los productos se purificaron por cromatografía en columna (CC, usando silica gel, hexano, disulfuro de carbono y cloroformo como fase móvil, a temperatura ambiente) y se caracterizaron por resonancia magnética nuclear (1H y 13C), infrarrojo con transformada de Fourier (FT-IR), espectroscopia UV-Visible, espectrometría de masas, desorción/ionización láser asistida por matriz - tiempo de vuelo (MALDI-TOF), voltametría cíclica (CV) y voltametría de onda cuadrada de Osteryoung (OSWV). Ambos compuestos mostraron picos de reducción irreversibles controlados por difusión, con niveles de energía LUMO de -3,09 eV y -3,13 eV para los monoadductos C60 y C70, respectivamente. Estos valores son comparables con el -3,99 eV de PC61BM. Los aductos sintetizados se incorporaron a las células solares de perovskita de tipo inversa y se usaron como materiales de transporte de electrones (ETM) obteniendo eficiencias de conversión de energía (PCE) de 8,5% y 14,0% para los monoaductos C60 y C70, respectivamente. Cuando el C60 se reemplaza por un fullereno menos simétrico como el C70, se observa una absorción de luz mejorada en la región visible.

Resumo Reportamos a sínteses de monoadutos de C60 e C70 a temperatura ambiente através da reação de Bingel, utilizando acetilacetona como ligando, na presença de DBU (1,8-diazabiciclo [5.4.0] undec-7-eno), tetrabromuro de carbono (CBr4) e o-diclorobenzeno. Foram obtidos monoadutos de diacetilmetano-[C60-IJ-fulereno-[5,6] e diacetilmetano-[C70-D5J-fulereno-[5,6] com rendimentos de 69% e 44%, respectivamente. Os produtos se purificaram por cromatografia em coluna (CC, usando sílica gel, hexano, dissulfeto de carbono e clorofórmio como fase móvel à temperatura ambiente ) e se caracterizaram por ressonância magnética nuclear OH e 13C), infra-vermelho com transformada de Fourier (FT-IR), espectroscopia UV-Visível, espectrometria de massas, ionização e dessorção a laser assistida por matriz-tempo de voo (MALDI-TOF), voltametria cíclica (CV) e voltametria de onda quadrada de Osteryoung (OSWV). Ambos compostos mostraram picos de redução irreversíveis controlados por difusão, com níveis de energia LUMO de -3,09 eV, -3,13 eV para os monoadutos C60 e C70, respectivamente. Estos valores são comparáveis com -3,99 eV de PC61BM. Os adutos sintetizados se incorporaram nas células solares de perovskita de tipo inversa e se usaram como materiais de transporte de eletrões (ETM) obtendo eficiências de conversão de energia (PCE) de 8,5% e 14,0% para os monoadutos C60 e C70, respectivamente. Quando o C60 se substitui por um fulereno menos simétrico como o C70, se observa uma absorção de luz melhorado na região visível.

Synthesis and Photophysical Study of [60]Fullerene-Maleimide Dyads.

Novel [60]fullerene-maleimide dyads were synthesized by covalent linking of maleimide fluorophore to the [60]fullerene (C60) via Bingel reaction. The dyads were well characterized and studied for their absorption and emission properties. The fluorescence quenching of maleimide moiety by C60 was observed, indicating the intramolecular energy transfer from maleimide fluorophore to C60 moiety.

Convenient syntheses of fullerynes for 'clicking' into fullerene polymers.

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition 'click' chemistry to form two fullerene polymers: one with C60 tethered to the end of a PS chain (C60-1PS) and the other with C60 tethered at the junction point of two PS chains of identical molecular weight (C60-2PS). The fullerene polymers were characterized by 1H NMR, 13C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C60 in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV-Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C60. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C60 content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.

Functionalization of fullerene via the Bingel reaction with α-chlorocarbanions: an ONIOM approach.

Two-layer ONIOM method at the ONIOM(B3LYP/6-31G(d):PM6) level of theory was applied to study the cycloaddition reaction of α-chlorocarbanions (CR2Cl(─), where R is H, Cl, CH3 CN, and NO2) and fullerene. The results show that the reaction pathways depend on the electron withdrawing functional groups or the electron donating functional groups contained in the α-chlorocarbanions. The energy profile analysis reveals that functionalization of fullerene by CCl3 (─), C(CH3)2Cl(─), and CH2Cl(─) is more favorable than by C(CN)2Cl(─) and C(NO2)2Cl(─) in terms of the thermodynamic point of view.

Preparation of Diaminedicarboxyplatinum (II) Functionalized Single-Wall Carbon Nanotube via Bingel Reaction as a Novel Cytotoxic Agent.

Carbon nanotubes have unique properties like high stability, high surface to mass ratio and so on which make them suitable for medicinal purpose applications. Treatment of cancer by organoplatinum agents like Cisplatin has become unresponsive in most cases due to low distribution of drug in biological fluids, inability of drug to cross cellular membranes and low stability in biological environments. Recently, carbon nanotubes (CNT) have stimulated much interest to overcome these limitations. Herein, we report the preparation of single-wall carbon nanotube functionalized by diaminedicarboxyplatinum (II) as an analogy of SWCNT-based Carboplatin. Functionalization was started by cyclopropanation through Bingel reaction and by use of diethylmalonate to yield cyclopropane-1,1-dicarboxy ethyl ester. Final product was obtained by hydrolysis of ester group and then chelation of platinum (IV) by dicarboxylate groups on the surface of SWCNT. Raman and Fourier transform -Infrared spectroscopy (IR), Thermogravimetric analysis (TGA) and energy dispers ive X-ray spectroscopy (EDAX) truly showed and confirmed the presence of the platinum (II) complex on the side wall of SWCNT. Cytotoxicity evaluation of the functionalized-SWCNTs on HeLa cells showed its higher anticancer ability than Cisplatin as indicated by IC50 value of 13 µg/mL.

Chemistry of C84 : Separation of Three Constitutional Isomers and Optical Resolution of D2 -C84 by Using the "Bingel-Retro-Bingel" Strategy.

The pure enantiomers of D2 -C84 as well as a third constitutional isomer of this higher fullerene were produced by a retro-Bingel reaction on the first organic derivatives of C84 (see scheme). These derivatives were synthesized by Bingel cyclopropenation of C84 , separated, and unambiguously structurally characterized.