碳电弧中~(#24106)C_(78)Cl_6的捕获与结构表征
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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~(#24106)C_(78)Cl_6,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~(#24106)C_(78)Cl_6与已有的氯化物~(#24106)C_(78)Cl_(18)、~(#24106)C_(78)Cl_(30)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.
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~(#24106 )C_(78)Cl_6conformed to the isolated pentagon rule was obtained.With X-ray single crystal diffraction,mass spectrometry and spectroscopy,~(#24106 )C_(78)Cl_(6 )was confirmed to have the same chlorine atom addition pattern as those of high chloride~(#24106 )C_(78)Cl_(18 )and~(#24106 )C_(78)Cl_(30 )at the[5,6,6]sites of the coronene segment.The capture of~(#24106)C_(78)Cl_6supported 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.
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~(#24106 )C_(78)Cl_6conformed to the isolated pentagon rule was obtained.With X-ray single crystal diffraction,mass spectrometry and spectroscopy,~(#24106 )C_(78)Cl_(6 )was confirmed to have the same chlorine atom addition pattern as those of high chloride~(#24106 )C_(78)Cl_(18 )and~(#24106 )C_(78)Cl_(30 )at the[5,6,6]sites of the coronene segment.The capture of~(#24106)C_(78)Cl_6supported 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.
引文
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[2] TAN Y Z,XIE S Y,HUANG R B,et al.The stabilization of fused-pentagon fullerene molecules[J].Nat Chem,2009,1(6):450-460.
[3] POPOV A A,YANG S,DUNSCH L.Endohedral fullerenes[J].Chem Rev,2013,113(8):5989-6113.
[4] HEATH J R.Synthesis of C60from 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.
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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-pentagonfused chlorofullerenes[J].Angew Chem Int Ed,2008,47(29):5340-5343.
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[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:apristine fullerene with favorable pentagon-adjacent structure[J].J Am Chem Soc,2010,132(48):17102-17104.
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[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 strainrelief pattern to stabilize fullerenes containing triple directly fused pentagons[J].Chem Asian J,2012,7(9):2036-2039.
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