Abstract

3′,3′-Bis-acetyl 3′H-cyclopropa[1,9](C₆₀-I_h)[5,6]fullerene and 3′,3′-Bis-acetyl 3′H-cyclopropa[8,25](C₇₀-D_5h(6))[5,6]fullerene monoadducts were obtained at room temperature via Bingel cyclopropanation reaction employing acetylacetone as ligand, DBU as base, carbon tetrabromide as intermediate for in situ formation of a bromomalonate and o-dichlorobenzene as solvent. Monoadducts were obtained with yields of 69% and 44% for C₆₀ and C₇₀ fullerene cages, respectively, and were purified on column chromatography by using silica gel as stationary phase and hexane, carbon disulfide (CS₂) and chloroform (CHCl₃) as mobile phase at r.t. Products were characterized by ¹H-NMR and ¹³C-NMR spectroscopy, FT-IR, and UV-visible spectroscopies, MALDI-TOF mass spectrometry, OSWV and cyclic voltammetry (CV). Products exhibited irreversible reduction peaks controlled by diffusion processes in the interface of the probed cell, with LUMO energy levels of –3.9 eV and –3.13 eV for C₆₀ and C₇₀ monoadducts, respectively. These values are comparable with –3.09 eV of PC₆₁BM employed as standard. The obtained adducts were incorporated into inverted-type perovskite solar cells and were used as electron transporting materials giving power conversion efficiencies (PCE) of 8.5% and 14% for C₆₀ and C₇₀ monoadducts, respectively. It was observed that absorption in the visible spectrum improves replacing C₆₀ fullerene by a fullerene with less symmetry, like C₇₀.

摘要

3'，3'-二乙酰3' ħ -cyclopropa [1,9]（C ₆₀ -我_ħ）[5,6]富勒烯和3'，3'-二乙酰3' ħ -cyclopropa [8， 25.（C ₇₀ - D _5h（6））[5,6]富勒烯单加合物在室温下通过Bingel环丙烷化反应获得，该反应使用乙酰丙酮作为配体，DBU作为碱，四溴化碳作为中间体原位形成溴代丙二酸酯和邻苯二酚。 -二氯苯作为溶剂。获得单加合物，C ₆₀和C _70的产率分别为69％和44％在室温下，分别使用硅胶作为固定相和正己烷，二硫化碳（CS ₂）和氯仿（CHCl ₃）作为流动相在柱色谱上纯化富勒烯笼，并通过¹ H-NMR和¹³ C- NMR光谱，FT-IR和紫外可见光谱，MALDI-TOF质谱，OSWV和循环伏安法（CV）。产品在被测电池的界面上表现出不可逆的还原峰，受扩散过程控制，对于C ₆₀和C ₇₀单加合物，LUMO能级分别为–3.9 eV和–3.13 eV 。这些值可与PC _61的–3.09 eV相比BM是标准配置。将获得的加合物掺入倒置型钙钛矿太阳能电池中，并用作电子传输材料，对于C ₆₀和C ₇₀单加合物，其功率转换效率（PCE）分别为8.5％和14％。观察到，在可见光谱中的吸收改善了用具有较少对称性的富勒烯（如C _70）代替C ₆₀富勒烯。