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[1]钟圆圆,田寒蕊,姚阳榕,等.碳电弧中#24106C78Cl6的捕获与结构表征[J].厦门大学学报(自然科学版),2019,58(01):27-33.[doi:10.6043/j.issn.0438-0479.201807016]
 ZHONG Yuanyuan,TIAN Hanrui,YAO Yangrong,et al.Capture and structure characterization of #24106C78Cl6 in carbon arc[J].Journal of Xiamen University(Natural Science),2019,58(01):27-33.[doi:10.6043/j.issn.0438-0479.201807016]
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碳电弧中#24106C78Cl6的捕获与结构表征(PDF/HTML)
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《厦门大学学报(自然科学版)》[ISSN:0438-0479/CN:35-1070/N]

卷:
58卷
期数:
2019年01期
页码:
27-33
栏目:
研究论文
出版日期:
2019-01-24

文章信息/Info

Title:
Capture and structure characterization of #24106C78Cl6 in carbon arc
文章编号:
0438-0479(2019)01-0027-07
作者:
钟圆圆田寒蕊姚阳榕张 欣石祥美张美林谢素原*黄荣彬郑兰荪
厦门大学化学化工学院,固体表面物理化学国家重点实验室,福建 厦门 361005
Author(s):
ZHONG YuanyuanTIAN HanruiYAO YangrongZHANG XinSHI XiangmeiZHANG MeilinXIE Suyuan*HUANG RongbinZHENG Lansun
State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China
关键词:
富勒烯 电弧放电 晶体结构 独立五元环规则 形成机制
Keywords:
fullerenes arc discharge crystallographic structure isolated pentagon rule formation mechanism
分类号:
O 613.42; O 613.71
DOI:
10.6043/j.issn.0438-0479.201807016
文献标志码:
A
摘要:
碳电弧放电法是合成富勒烯及其衍生物的最重要方法之一,但电弧反应过程复杂,涉及的衍生化机制尚不明确.采用电弧法合成含有氯化富勒烯的碳灰,借助高效液相色谱法对其进行分离、纯化,得到了符合独立五元环规则的氯化富勒烯#24106C78Cl6,结合X-射线单晶衍射、质谱、紫外-可见吸收光谱对其进行结构表征,证明#24106C78Cl6与已有的氯化物#24106C78Cl18#24106C78Cl30在六并苯片段具有相同的氯原子加成[5,6,6]位点,同时也证明了在氯参与的碳电弧中,富勒烯在靠近电弧中心的较高温区发生氯化反应,而氯化碳簇的加成反应发生于更低的温区.
Abstract:
Arc discharge of carbon was one of the most important methods for the synthesis of fullerenes and their chlorinated derivatives.However,the arc reaction process was complicated and the involved derivatization mechanism was still unclear.Herein the carbon ash containing chlorinated fullerenes was synthesized using the carbon arc.Separated and purified with high performance liquid chromatography,the chlorinated fullerene #24106C78Cl6 conformed to the isolated pentagon rule was obtained.With X-ray single crystal diffraction,mass spectrometry and spectroscopy,#24106C78Cl6 was confirmed to have the same chlorine atom addition pattern as those of high chloride #24106C78Cl18 and #24106C78Cl30 at the [5,6,6] sites of the coronene segment.The capture of #24106C78Cl6 supported that the chlorination reaction occurred in the higher temperature zone near the center of the arc,whereas the addition reaction of the chlorinated carbon cluster occurred in the lower temperature zone in the complex chlorine-involving carbon arc.

参考文献/References:

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[3] POPOV A A,YANG S,DUNSCH L.Endohedral fullerenes[J].Chem Rev,2013,113(8):5989-6113.
[4] HEATH J R.Synthesis of C60 from small carbon clusters[J].ACS Symp Ser,1992,481:1-23.
[5] HUA X,CAGIN T,CHE J,et al.QM(DFT)and MD studies on formation mechanisms of C60 fullerenes[J].Nanotechnology,2000,11(2):85-88.
[6] KHAN S D,AHMAD S.Modelling of C2 addition route to the formation of C60[J].Nanotechnology,2006,17(18):4654-4658.
[7] CURL R F,LEE M K,SCUSERIA G E.C60 buckminster fullerene high yields unraveled[J].J Phys Chem A,2008,112(46):11951-11955.
[8] SAHA B,IRLE S,MOROKUMA K.Hot giant fullerenes eject and capture C2 molecules:QM/MD simulations with constant density[J].J Phys Chem C,2011,115(46):22707-22716.
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[13] HAN X,ZHOU S J,TAN Y Z,et al.Crystal structures of saturn-like C50Cl10 and pineapple-shaped C64Cl4:geometric implications of double- and triple-pentagon-fused chlorofullerenes[J].Angew Chem Int Ed,2008,47(29):5340-5343.
[14] TAN Y Z,HAN X,WU X,et al.An entrant of smaller fullerene:C56 captured by chlorines and aligned in linear chains[J].J Am Chem Soc,2008,130(46):15240-15241.
[15] TAN Y Z,LIAO Z J,QIAO Z Z,et al.Two Ih-symmetry-breaking C60 isomers stabilized by chlorination[J].Nat Mater,2008,7(10):790-794.
[16] TAN Y Z,LI J,ZHU F,et al.Chlorofullerenes featuring triple sequentially fused pentagons[J].Nat Chem,2010,2(4):269-273.
[17] TAN Y Z,ZHOU T,BAO J,et al.C72Cl4:a pristine fullerene with favorable pentagon-adjacent structure[J].J Am Chem Soc,2010,132(48):17102-17104.
[18] TAN Y Z,CHEN R T,LIAO Z J,et al.Carbon arc production of heptagon-containing fullerene[68][J].Nat Commun,2011,2:420.
[19] ZHOU T,TAN Y Z,SHAN G J,et al.Retrieving the most prevalent small fullerene C56[J].Chemistry,2011,17(31):8529-8532.
[20] SHAN G J,TAN Y Z,ZHOU T,et al.C64Cl8:a strain-relief pattern to stabilize fullerenes containing triple directly fused pentagons[J].Chem Asian J,2012,7(9):2036-2039.
[21] TAN Y Z,LI J,DU M Y,et al.Exohedrally stabilized C70 isomer with adjacent pentagons characterized by crystallography[J].Chem Sci,2013,4(7):2967-2970.
[22] GAO C L,LI X,TAN Y Z,et al.Synthesis of long-sought C66 with exohedral stabilization[J].Angew Chem Int Ed,2014,53(30):7853-7855.
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[26] TAMM N B,KOSAYA M P,FRITZ M A,et al.Synthesis,isolation,and X-ray structural characterization of trifluoromethylated C78 fullerenes:C78(2)(CF3)10/12 and C78(3)(CF3)12/14[J].Nanosystems:Physics,Chemistry,Mathematics,2016:111-117.doi:10.17586/2220-8054-2016-7-1-111-117.
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[31] TROYANOV S I,KEMNITZ E.The first crystal structure of a halogenated higher fullerene,C78Br18,obtained by bromination of a fullerene mixture[J].Eur J Org Chem,2003,2003(20):3916-3919.
[32] TROYANOV S I,TAMM N B,CHEN C,et al.Synthesis and structure of a highly chlorinated C78:C78(2)Cl30[J].Z Anorg Allg Chem,2009,635(12):1783-1786.
[33] KOSAYA M P,FRITZ M A,BROTSMAN V A,et al.Synthesis,isolation and structure of trifluoromethylated fullerene D3-C78,C78(1)(CF3)10-18[J].Chem Asian J,2016,11(7):1000-1003.
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[35] OLMSTEAD M M,DE BETTENCOURT-DIAS A,DUCHAMP J C,et al.Isolation and structural chara-cterization of the endohedral fullerene Sc3N@C78[J].Angew Chem Int Ed,2001,40(7):1223-1225.
[36] CAO B P,WAKAHARA T,TSUCHIYA T,et al.Isolation,characterization,and theoretical study of La2@C78[J].J Am Chem Soc,2004,126(30):9164-9165.
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备注/Memo

备注/Memo:
收稿日期:2018-07-10 录用日期:2018-08-19
基金项目:国家自然科学基金(51572231,21721001)
*通信作者:jxmu_syxie@xmu.edu.cn
更新日期/Last Update: 1900-01-01