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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photochemical Generation of Polymeric Alkyl-C_(60) Radicals:ESR Detection and Identification
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Photochemical Generation of Polymeric Alkyl-C_(60) Radicals:ESR Detection and Identification

机译：聚合烷基-C_（60）自由基的光化学生成：ESR检测与鉴定

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摘要

Electron spin resonance (ESR) spectroscopy has been used to study various alkylfullerene radical adducts generated by UV-photoinitiated reactions between low-density polyethylene (LDPE) and C_(60) in the presence or absence of benzophenone (BP) as a photoinitiator under different conditions. Photolysis of LDPEIBP/C_(60) mixture in toluene at 323 K produced benzylfullerene (RC_(60)) radical adducts, showing a strong ESR signal of g = 2.002 70 with several well-resolved pairs of~(13)C satellites. On the other hand, a well-resolved ESR spectrum characteristic of polymeric alkylfullerene (PC_(60)) radical adducts was observed during UV irradiation of the LDPEIBP/C_(60) in benzene or in the molten state (413 K). Detailed analyses of hyperfine structures (hfs) revealed that the ESR spectrum for PC6o radical adducts consisted of three components: (1) a broad singlet at g = 2.002 50 arising from C_(60) radical anions; (2) an innermost pair of ~(13)C satellites; and (3) a 12-line spectrum superimposed on the broad singlet. Spectroscopic simulation allowed the 12-line spectrum to be attributed to the coexistence of two polymeric radical adducts of C_(60) (i.e., the tertiary carbon radical adduct(CH_2)_3C-C_(60)~., designated as PAC_(60)~., and the secondary carbon radical adduct, -(CH_2)_2CH-C_(60)~., designated as P_BC_(60)), which have slightly different g values (gA. = 2.002 48 and gB 2.00244) and integral intensities I_A/l_B (48.4/51.6). These results clearly indicated the generation of C_(60)-bonded LDPE materials simply by photoirradiation of LDPE/C_(60) with BP as a photoinitiator.
机译：电子自旋共振（ESR）光谱已用于研究在存在或不存在二苯甲酮（BP）作为光引发剂的情况下，低密度聚乙烯（LDPE）和C_（60）之间通过UV光引发的反应由紫外线引发的各种烷基富勒烯自由基加合物条件。 LDPEIBP / C_（60）混合物在323 K下甲苯中的光解产生了苄基富勒烯（RC_（60））自由基加合物，其具有几对分辨良好的〜（13）C卫星对，显示g = 2.002 70的强ESR信号。另一方面，在苯或熔融态（413 K）下对LDPEIBP / C_（60）进行紫外线照射期间，观察到聚合物烷基富勒烯（PC_（60））自由基加合物的良好分辨的ESR光谱特征。对超精细结构（hfs）的详细分析表明，PC60自由基加合物的ESR谱图由三部分组成：（1）g = 2.002 50的宽单重峰，源自C_（60）自由基阴离子; （2）一对最里面的〜（13）C卫星; （3）在宽单峰上叠加了12行谱。光谱模拟允许12行谱归因于C_（60）的两个聚合自由基加合物的共存（即叔碳自由基加合物（CH_2）_3C-C_（60）〜。，称为PAC_（60） 〜和二级碳自由基加合物-（CH_2）_2CH-C_（60）〜。，称为P_BC_（60）），它们的g值（gA。= 2.002 48和gB 2.00244）和积分强度略有不同I_A / l_B（48.4 / 51.6）。这些结果清楚地表明简单地通过用BP作为光引发剂对LDPE / C_（60）进行光辐照来产生C_（60）键合的LDPE材料。

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