富勒烯[60]-3,5-二氯-4-吡啶酮衍生物的合成研究

以3,5-二氯-4-吡啶酮为原料,与对甲苯磺酰肼发生缩合反应生成3,5-二氯-4-吡啶酮对甲苯磺酰腙、再与富勒烯[60]发生[2+1]环加成反应,制备了富勒烯[60]-3,5-二氯-4-吡啶酮衍生物,总产率35.6%。探索了富勒烯[60]与酰腙发生环加成反应的最佳工艺条件。产物结构经IR,1HNMR,MS表征。     

吸电子基团对[60]富勒烯吡咯烷空间结构的理论研究

借助密度泛函量子力学程序对硝基、甲氧基和羟基3种吸电子基团对[60]富勒烯吡咯烷空间结构的影响进行了研究。结果表明,结构优化后的[60]富勒烯吡咯烷衍生物的LUMO与HOMO能量差ΔE并不随基团吸电子能力的增强而增加,吸电子基团对[60]富勒烯衍生物吡咯烷键长和键角的影响大小为NO2>OH>OCH3。     

富勒烯[60]-曲酸衍生物的合成

富勒烯[60]是由相邻的六元环和五元环组合而成的中空状球形分子,环中含有30个双键,具有缺电子烯烃性质,易发生加成反应。文章通过对甲苯磺酰肼与曲酸缩合反应生成曲酸对甲苯磺酰腙,再与富勒烯[60]发生环加成反应合成了富勒烯[60]-曲酸衍生物,产率32%。目标产物的结构经IR、1H NMR、MS确认。     

富勒烯羰基内酰胺化合物的亲电芳香取代反应研究

氮杂富勒烯是目前被重点关注的一类杂富勒烯,在化学合成方法中均需要经过开孔衍生物,然而对于氮杂富勒烯的前体开孔化合物—羰基内酰胺衍生物,人们的研究报道较少。本研究对其与富电子芳烃的亲电芳香取代反应进行了系统的研究。研究发现,反应除了生成单取代芳基氮杂[60]富勒烯,还有两个副产物。本论文对两个副产物进行了详细的表征和结构鉴定,这对后续开展氮杂富勒烯的深入研究提供了有利条件。     

富勒烯储氧技术研究进展

对[60]富勒烯储氢技术的储氢原理和储氢方式进行了概述,重点阐述了[60]富勒烯2种重要的储氢方式(笼内储氢和笼外储氢)的国内外研究进展,最后对[60]富勒烯储氢技术的发展以及[60]富勒烯储氢材料的应用进行了展望.     

微波辐射下[60]富勒烯与脱氢枞胺的加成反应

在N2保护下,脱氢枞胺(C20H31N)被四醋酸铅氧化生成的氮烯活性中间体与[60]富勒烯(C60)在氯苯溶剂中,用微波加热至130℃,反应2 h,发生[1+2]氮烯环加成反应.通过硅胶柱层析分离提纯反应混合物,得到脱氢枞胺与C60的氮烯环加成衍生物,得率为59.4%(基于已反应的C60).通过FT-IR、13C NMR、1H NMR、MALDI-TOF-MS等分析方法对该衍生物进行了结构测定,证实其主要成分为预期的单加成结构,同时存在少量的二加成结构.将微波辐射下的反应与传统的热条件下的反应进行了对比,结果表明,微波辐射可以缩短加成反应的时间,并且能有效地提高反应得率.     

聚合物太阳能电池富勒烯衍生物受体材料的制备及其表征

作为新能源,由于有机太阳能电池具有量轻、易于大面积柔性制备等特点,最近有机聚合物太阳能电池的开发得到了越来越多的关注,其光电转化效率最高值不断被刷新,这也带动了新材料的研发。本论文设计并合成了2个噻吩-富勒烯(C60)二元结构的化合物,用作电池的受体活性材料,进一步可开发成D-A型活性材料。通过利用活性的丙二酸亚异丙酯为起始原料,与十二醇进行酯化反应,高收率的制备了丙二酸单十二烷基酯中间体,再与5,5-二羟甲基环戊[c]并噻吩反应,生成对称的丙二酸双酯,最后与富勒烯C60进行Bingel反应制备2个富勒烯衍生物,其电化学性质被表征。     

齐聚噻吩/C60双电缆共聚物的合成及结构表征

可溶性聚噻吩和富勒烯(主要是C60)及其衍生物,是聚合物太阳能电池中被广泛使用的给体和受体材料[1~3],二者之间的相容性和富勒烯的聚集效应是影响光电转换效率的主要因素[4]。本文中,用Suzuki偶联法逐步合成噻吩的齐聚物,并通过氮卡宾反应将富勒烯和齐聚噻吩用共价键键接在一起,得到单一分子量分布的齐聚噻吩/C60共聚物,可实现分子水平的相连续结构。另外,通过1H-NMR、MALDI-ToF MS手段对其结构进行表征,通过循环伏安测试表征噻吩单元和C60在基态并无相互作用,紫外可见吸收光谱表明在300-500nm处有一个明显的吸收带。     

含长碳链富勒烯衍生物的制备与表征

为了改善有机太阳能电池的光电特性,本文设计一种溶解性良好的富勒烯衍生物作为电池的受体材料。以对苯二酚和溴代正辛烷为原料制备对辛烷氧基苯酚中间体,再与丙二酸环亚异丙酯反应合成丙二酸单酯,进一步与十二醇酯化合成不对称丙二酸双酯,最后与富勒烯(C60)进行Bingel反应制备了含长碳链的富勒烯衍生物目标物,该化合物结构与电化学性质完全被表征。     

有机太阳能电池用受体材料的制备

本研究对富勒烯C60进行化学改性,合成的材料用于聚合物太阳能电池的受体材料。首先以对苯二酚和溴代正辛烷为起始原料,制备出对辛烷氧基苯酚,再与丙二酸亚异丙酯进行酯化反应,合成不对称性的丙二酸单酯,并进一步与含羟基化合物反应,生成不对称丙二酸双酯,最后与富勒烯C60进行Bingel反应制备出含长碳链的富勒烯衍生物。作为潜在的光电材料,其光电特性经CV和UV表征。     

C60衍生物在金表面的自组装

利用叠氮化反应和[4+2]环加成反应合成了含2, 2?:6?,2?–三联吡啶基团的C60衍生物. 研究了它在Au(111)面上的自组装，STM研究发现，可以在Au(111)面上形成较高质量的单层膜. 同时研究了它在金纳米粒子表面的自组装, 发现可以通过调节搅拌速度来获得不同粒径的金纳米粒子，搅拌速度越快金纳米粒径越小，而用超声波振荡也可获得较小粒径的金纳米粒子.     

[60]富勒烯[2+1]环加成反应研究进展

对[60]富勒烯的[2 1]环加成反应、主要试剂及反应机理进行了综述。     

Synthesis, characterization and modification of azide-containing dendronized diblock copolymers

A series of dendronized diblock copolymers having rigid backbone and reactive surface were synthesized by ring-opening metathesis polymerization (ROMP) from dendronized norbornene derivatives using the second generation Grubb's catalyst. The bromine-terminated block of those rigid nanostructures has been converted to more reactive azide groups in one straightforward step. The resulting polymers were then functionalized by post-polymerization reaction with fullerene C₆₀ (electron acceptor) using thermal [3 + 2] cycloaddition reaction or with porphyrin (electron donor) using copper-catalyzed “click chemistry”, the ultimate goal being the preparation of efficient polymeric materials for photovoltaic applications. While fullerene addition was not complete (approximately 50%) because of cross-linking reactions and steric hindrance on the dendrimers surface, Zn-porphyrin introduction went to completion clearly demonstrating the usefulness of click chemistry for polymer functionalization.     

Rh-Catalyzed Cycloaddition of C60 with Enynes: Unveiling the Mechanistic Pathway

In this study we present a method for functionalizing C₆₀ through a Rh-catalyzed cyclization reaction with 1,6-enynes, resulting in the formation of a fused bicyclic structure. Additionally, fullerene derivatives are further functionalized through regioselective photooxygenation reactions. Our DFT calculations reveal two distinct reaction pathways: one involving rhodium-catalyzed cycloisomerization of the enyne followed by Diels-Alder with C₆₀, and the other featuring a rhodium-catalyzed [2+2+2] cycloaddition of enyne and C₆₀ followed by isomerization. Surprisingly, both pathways exhibit nearly identical energy barriers. However, experimental tests indicate that the predominant pathway varies depending on the substitution motifs of the substrates.     

Synthesis and characterization of new C60-PPV dyads containing carbazole moiety

New C₆₀ covalently linked PPV derivatives containing carbazole moiety poly{(2,5-di-pentoxyl-phenylene)-1,4-diylvinylene-3,6-[9-(1-azafulleroid-propyl)carbazolenevinylene]} (PPV-AFCAR) were synthesized and characterized. The polymers containing different percentage of C₆₀ were obtained through the percentage of azido unit being controlled by the initial feed ratio. Cyclic voltametric analysis showed that the electronic characteristic remained while it covalently attached to polymer by the cycloaddition reaction. The fluorescences of PPV moieties were strongly quenched due to the presence of fullerene.     

Multifunctional hybrid materials composed of [60]fullerene-based functionalized-single-walled carbon nanotubes

We report the synthesis and characterization of several hybrid [60]fullerene-SWCNT materials that combine [60]fullerenes with appended photoactive ferrocenyl or porphyrinyl functionalities and SWCNTs into a single multifunctional structure, where the dyads are covalently attached to the exo-surface of SWCNTs. The structural properties of all hybrids have been characterized using a large variety of spectroscopic and HR-TEM techniques. Raman spectra showed how all SWCNTs were functionalized and the presence of functional groups in the nanotube derivatives. Furthermore, these spectra reveal a new electronic activity of the compounds due to the interaction of the functional groups with the SWCNT frameworks. XPS investigations have documented the presence of [60]fullerene derivatives around the exo-surface of the oxidized SWCNT walls, exhibiting a characteristic photoelectron N 1s emission peak at 400.3 eV. Very importantly, by means of HR-TEM investigations we have also observed the presence of the [60]fullerene functions on the SWCNT outer surface by imaging spherical structures. The presence of the porphyrinyl and ferrocenyl fragments, which can act as effective chromophores and electroactive species, makes this class of materials very interesting for applications in optoelectronics and photovoltaics, and bio-applications, for example in the field of diagnosis and treatment.     

Fullerene lipids: Synthesis of novel nitrogen-bridged [60]fullerene fatty ester derivatives

Reactions of methyl 6-azido-hexanoate, 8-azido-octanoate, and 12-azido-dodecanoate with [60]fullerene (1) gave the corresponding aza-[60]fullerene ester derivatives (2a-2c, 22–35% based on the amount of [60]fullerene reacted). The nitrogen atom is bonded to the [60]fullerene cage to yield a “[5,6]-open” type aza substructure. This was confirmed by the appearance of 30–31 sp ² signals at δ_C 133–147 in the carbon nuclear magnetic resonance spectra. Reaction of methyl 11-azido-7-undecynoate with [60]fullerene furnished a mixture of aza-[60]fullerene (2d, 53%) and aziridine-[60]fullerene (2e, 38%) ester derivatives. Compound 2e was identified as the “[6,6]-closed” type aziridine-[60]fullerene derivative, which displayed 10 sp ² signals in the region δ_C 140–145 and one signal at δ_C 85.05 for the sp ³ carbons of the cage. Refluxing a solution of compound 2d in toluene for 50 h gave about 50% yield of compound 2e, but not vice versa.     

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.     

Fullerene lipids: Synthesis of C60 fullerence derivatives bearing a long-chain saturated or unsaturated triester system

Tris(hydroxymethyl)aminomethane was successfully esterified with saturated and unsaturated long-chain fatty acids. The resulting amino-triester intermediates were successively reacted with chloroacetyl chloride, sodium azide, and C₆₀ fullerene. Spectral evidence showed that the aziridine ring is joined to the junction of [6,6]-fused rings of the fullerene. The structures of the various C₆₀ fullerene derivatives bearing a long-chain saturated or unsaturated triester system were characterized by spectroscopic and spectrometric methods.     

Study of the Desensitizing Effect of Different [60]Fullerene Crystals on Cyclotetramethylenetetranitramine (HMX)

Three types of [60]fullerene crystals were obtained. The first one was the direct commercial [60]fullerene, and the other two were recrystallized from the first one in carbon bisulfide and in carbon bisulfide/petroleum ether, respectively. Scanning electron microscopy (SEM), X‐ray powder diffractometry (XRD), and FT‐IR spectrometry were used to study the physical characteristics of the crystals. The thermal stability of the three [60]fullerene crystals was studied by differential thermal analysis (DTA), and the effects of the three [60]fullerenes on the mechanical sensitivity and friction sensitivity of HMX were tested and analyzed. It was found that the three types of [60]fullerenes have different thermal stabilities, and the friction and impact sensitivities of HMX are reduced from 100% to 70% and to 60%, respectively when 1% [60]fullerene 3 was added in HMX.