C70苄基衍生物的合成及其在钙钛矿太阳能电池中的应用

富勒烯及其衍生物具有高的电子传输效率,是倒置平面异质结钙钛矿太阳能电池器件中优异的电子传输层材料（electron transport materials, ETMs）。其中,富勒烯C70通常存在众多的异构体产物,通过常规的手段难以实现有效分离,故关于结构明确的富勒烯衍生物对钙钛矿太阳能电池的影响,目前尚缺乏系统的研究和理解。本文基于对一种结构明确的C70衍生物2,5-（PhCH2）2C70的成功合成和分离,并将其作为电子传输材料构建平面异质结倒置太阳能电池器件,最终实现了12.77%的光电转换效率,通过对富勒烯衍生物中分子的晶体结构堆积的研究,分析富勒烯衍生物结构对钙钛矿太阳能电池器件性能的影响。该工作对于拓展和丰富富勒烯衍生物在钙钛矿电池中的应用有着重要的意义。国家重点基础研究发展计划(973计划)(2014CB845601,2015CB932301);;\n国家自然科学基金(21771152,21721001,21390390,51572231,21701134);;\n福建省科技厅高校产学合作项目(2016H6023);;\n中央高校基本科研业务费(20720170028,20720160084

Flexible decapyrrylcorannulene hosts

球形笼状的富勒烯是上个世纪末最重要的科学发现之一，但对富勒烯的精确几何结构的认识却困难重重，原因是单晶中球形分子的取向往往是无序的，需通过笼外衍生或通过八乙基金属卟啉-富勒烯超分子主客体组装来固定富勒烯的取向，然后利用常用的单晶衍射分析技术来精确表征富勒烯的几何结构。然而许多富勒烯新结构因无法与卟啉主体形成高质量的单晶至今仍无法利用X射线衍射技术进行结构分析，直接制约了对富勒烯形成机理及结构-性能关系的深入认识。功能团簇材料创新研究群体的谢素原、张前炎课题组另辟蹊径地从曲面结构的十氯碗烯C20Cl10出发，合成了十吡咯取代的碗烯分子C20(C4H4N)10。结构分析表明该分子的结构特征是碗烯的碳框架与十个吡咯基团通过单键相连。实验还证明，用甲基去取代吡咯3, 4-位置的氢并不利于富勒烯与碗烯衍生物形成有序的超分子组装体，理论研究进一步诠释了十个吡咯‘手指’的集体贡献比单个碗烯‘手掌’更大的原因。该研究工作是功能团簇材料创新研究群体长期积累，并由校内外十多位研究人员共同努力完成。徐云彦（2014级硕士生）、田寒蕊（2014级博士生）和李姝慧（2016年进站博士后）为该论文共同第一作者。【Abstract】The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement. Here we show a chiral configuration of decapyrrylcorannulene that has a concave ‘palm’ of corannulene and ten flexible electron-rich pyrryl group ‘fingers’ to mimic the smart molecular ‘hands’ for self-adaptably cradling various buckyballs in a (+)hand-ball-hand(−) mode. As exemplified by crystallographic identification of 15 buckyball structures representing pristine, exohedral, endohedral, dimeric and hetero-derivatization, the pyrryl groups twist with varying dihedral angles to adjust the interaction between decapyrrylcorannulene and fullerene. The self-adaptable electron-rich pyrryl groups, susceptible to methylation, are theoretically revealed to contribute more than the bowl-shaped palm of the corannulene in holding buckyball structures. The generality of the present decapyrrylcorannulene host with flexible pyrryl groups facilitates the visualization of numerous unknown/unsolved fullerenes by crystallography and the assembly of the otherwise close-packed spherical fullerenes into two-dimensional layered structures by intercalation.This research was supported by the National Natural Science Foundation of China (21771152, 21721001, 21827801, 51572231, 51572254, 21571151, 2170010228), the 973 Program of China (2014CB845601 and 2015CB932301), the China Postdoctoral Science Foundation (2016M602067), the National Key Research and Development Program of China (2017YFA0402800), and the Fundamental Research Funds for the Central Uni- versities (20720170028, 20720160084). Q.Y.Z. is particularly grateful to 21771152, 2015CB932301, 20720170028, 20720160084; S.F.Y. is particularly grateful to 51572254 and 2017YFA0402800; S.Y.X. is particularly grateful to 21721001 and 51572231; L.S.Z. is particularly grateful to 21827801; S.L.D. is particularly grateful to 21571151; S.H.L. is particularly grateful to 2170010228 and 2016M602067. 研究工作得到国家自然科学基金（21771152、21721001、21827801、51572231、51572254, 21571151、2170010228）、科技部973计划（2014CB845601、2015CB932301）和重点研发计划（2017YFA0402800）、国家博士后科学基金、中央高校基本科研业务费等的资助

Rational synthesis of an atomically precise carboncone under mild conditions

在已知的碳的存在形态中，还有一种锥型的碳结构，早在50年前人们在热解碳时发现了这类结构，此前也常被人们称为碳纳米锥，虽然这类碳纳米锥有望作为扫描隧道显微镜的探针、场发射头等替代材料，但始终未能找到合适方法精准地合成它们。因此，这类锥型碳材料尚未得到人们足够重视和开发。功能团簇材料创新研究群体的谢素原、张前炎课题组与美国波士顿学院的Lawrence Scott教授合作，首次通过有机合成途径，在温和的条件下合成得到了首例结构明确的碳锥单元（碳锥子）C70H20及其可溶衍生物。他们通过实验、理论计算、结构分析，最终在他们合成的碳锥子结构中，仅有1个五元环在锥顶，而在锥顶和锥缘之间（围绕着中心五元环）有2圈由六元环组成的完整的稠圈层，谢素原等将这一碳锥子命名为carboncone[1,2]。通过这一典型的碳锥子（carboncone[1,2]），有望借助气相沉积等技术不断增加稠圈层数（m）来制备具有确定锥角的系列单壁纳米碳锥（carboncone[1,m>2]）。随着研究的深入，不久的将来人类有望合成出其它四种不同锥角的碳锥子（carboncone[n=2-5,m]），完整地研究探索和开发利用这类锥型结构的碳材料。 化学化工学院2015级硕士生朱正钟（主要负责合成）和2017级博士生陈佐长（主要负责理论计算）为该论文的共同第一作者。Carboncones, a special family of all-carbon allotropes, are predicted to have unique properties that distinguish them from fullerenes, carbon nanotubes, and graphenes. Owing to the absence of methods to synthesize atomically well-defined carboncones, however, experimental insight into the nature of pure carboncones has been inaccessible. Herein, we describe a facile synthesis of an atomically well-defined carboncone[1,2] (C70H20) and its soluble penta-mesityl derivative. Identified by x-ray crystallography, the carbon skeleton is a carboncone with the largest possible apex angle. Much of the structural strain is overcome in the final step of converting the bowl-shaped precursor into the rigid carboncone under mild reaction conditions. This work provides a research opportunity for investigations of atomically precise single-layered carboncones having even higher cone walls and/or smaller apex angles.This research was supported by the National Natural Science Foundation of China (21771152, 21721001, 21390390, 21827801, 51572231, 21571151, and 21701134), the 973 Program of China (2015CB932301), the Major Science and Technology Project between University-Industry Cooperation in Fujian Province (2016H6023), and the Fundamental Research Funds for the Central Universities (20720170028 and 20720160084). This research was also supported financially by the U.S. National Science Foundation (CHE-0809494 and CHE-1149096). 研究工作得到国家自然科学基金（21771152等）、科技部重大科学研究计划项目（2015CB932301）和福建省高校产学合作项目、中央高校基本科研业务费、美国国家科学基金等的资助

AlCl3/ICl催化合成十氯代碗烯(C20Cl10)

卤代碗烯因其碳卤键具有较高的化学反应活性,被认为是碗烯化学研究中一类非常重要的反应中间体.将三氯化铝和一氯化碘进行组合,提出了一种合成十氯代碗烯的新方法.与已报道的十氯代碗烯合成方法相比,该方法不需要在无水无氧的苛刻反应条件下进行,操作简单,而且将产率由文献报道的60%提高到96%.制备得到的十氯代碗烯可以成功转化为十苯硫基碗烯,证实了十氯代碗烯的确可以由新的氯化方法成功合成.该新型氯化方法为合成一些重要的碗烯衍生物提供了便利.国家自然科学基金(21771152);;中央高校基本科研业务费专项(20720170028,20720160084

刍议中西地理学传统的差异

本文对地理学史论著进行研究之后,比较了中国和希腊古代地理学的发展状况,论述了中西地理学传统的重大差异,并对形成这些差异的主要原因进行了探讨

Optimization of Synthesizing Aza[60]fullerene

氮杂富勒烯是目前唯一得到较为广泛研究的杂富勒烯,但较低的合成产率成为了制约其深入研究的主要障碍.本研究对比了氮杂[60]富勒烯的Wudl、gAn、HIrSCH等3种合成方法,并对Wudl法的影响因素进行了系统研究,经工艺优化,显著地抑制了从C60到羰基内酰胺中间产物合成过程中的副产物的生成,基于回收原料C60的羰基内酰胺中间产物产率达63.9%,氮杂[60]富勒烯的总产率由11.3%提高到20.9%,且过量C60可高效回收并直接使用.本研究基于对影响氮杂[60]富勒烯合成产率的因素的深入探讨,提出的工艺较Wudl法降低了氮杂[60]富勒烯的制备成本,为进一步探索氮杂富勒烯的性质规律和应用前景创造了有利条件.The azafullerenes are the only known heterofullerenes that have been investigated widely,typically exemplified by aza[60]fullerene,in which one or more carbons are substituted by nitrogen atom(s)in C60 cage.Extensive attention has been paid owing to its unique structure and reactive activities,but its in-depth study and application are restricted by its low yield.This paper summarized the research background and recent progress of azafullerenes,compared the three synthetic methods(Gan′s method,Hirsch′s method and Wudl′s method)for aza[60]fullerene dimer,and focused on optimizing the Wudl′s method systematically.Especially,the by-products in the conversion process from C60 to fulleroid had been inhibited efficiently.The yield of fulleroid had increased to63.9% based on recycling C60.The total yield of aza[60]fullerene had increased from 11.3%to 20.9%,and the excess C60 could be isolated and used again.This optimization reduced the cost of preparing aza[60]fullerene,and made the aza[60]fullerenes more easily available compared with Wudl′s method,which would create opportunities for probing more interesting nature and important application in the future study of azafullerenes.国家重点基础研究发展计划(973计划)(2014CB845601); 国家自然科学基金海峡联合基金项目(20131004

At Home Abroad : A memoir of the Ford Foundation in Indonesia, 1953-1973

自从作为富勒烯片段的心环烯分子被合成以来,大量具有C5对称性的碳-碳、碳-卤、碳-硼、碳-氧和碳-硫键修饰的心环烯衍生物陆续得到合成,然而具有C5对称性的碳-氮键修饰的心环烯衍生物至今还没有报道。本文通过五咔唑氮负离子对1,3,5,7,9-五氯心环烯的亲核取代反应实现了碳-氮键偶联并得到具有C5对称性的心环烯衍生物1,3,5,7,9-五咔唑基心环烯。该化合物的C5对称结构得到了核磁共振波谱、高分辨质谱的证实,其立体结构借助了密度泛函理论（DFT）计算模拟。咔唑基团作为一类富电子的含氮杂环,其衍生物表现出了许多优异的光电性能和生物活性,因此1,3,5,7,9-五咔唑基心环烯分子的成功合成不仅提供了一类新型的碳-氮键修饰的心环烯衍生物,而且该分子有可能在超分子、光电材料、生物方面具有重要的潜在应用

Synthesis of long-sought C66 with exohedral stabilization

Previously reported fused-pentagon fullerenes stabilized by exohedral derivatization do not share the same cage with those stabilized by endohedral encapsulation. Herein we report the crystallographic identification of #4348C66Cl10, which has the same cage as that of previously reported Sc2@C66. According to the geometrical data of #4348C66Cl10, both strain relief (at the fused pentagons) and local aromaticity (on the remaining sp 2-hybrided carbon framework) contribute to the exohedral stabilization of this long-sought 66 carbon atom cage. Captured at last! Elusive #4348C66 was stabilized exohedrally to give a fullerene derivative identified as #4348C66Cl10 by X-ray single-crystal diffraction (see picture). The isolation of this chlorofullerene supports the existence of #4348C66 in the carbon arc. ? 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim