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Rates of Ring Opening of Radical Cation Intermediates Govern Differences in Thermoluminescence between 1‐ and 2‐Naphthyl‐Substituted Methylenecyclopropanes
ChemPhotoChem ( IF 3.0 ) Pub Date : 2019-10-23 , DOI: 10.1002/cptc.201900230
Yasunori Matsui 1, 2 , Kazuki Shimono 1 , Kosuke Takae 1 , Hayato Namai 3 , Toshiki Sera 1 , Takuya Ogaki 1 , Eisuke Ohta 1, 2 , Kazuhiko Mizuno 1, 2 , Hiroshi Ikeda 1, 2
Affiliation  

In this study, we observed that methylenecyclopropane 1 c, possessing geminal phenyl and 1‐naphthyl groups at C‐2 of the three membered ring, emits green thermoluminescence (TL) in a low temperature matrix, associated with two sets of bands in the 480–600 and 600–700 nm regions. The bands are assigned to phosphorescence from 31 c* and triplet‐triplet (T−T) fluorescence (FL) from the corresponding trimethylenemethane biradical 32 c..*, respectively. In contrast, as previously reported, the analogous 2‐naphthyl derivative 1 b emits red TL associated with two bands in the 350–450 and 600–700 nm regions, which are assigned to FL from 11 b* and T−T FL from 32 b..*. The results of spectroscopic studies and density functional theory calculations show that the observed dissimilarity in the TL properties of 1 b and 1 c is a consequence of differences in the rate of methylenecyclopropane ring opening of 1 b.+ and 1 c.+ associated with stereoelectronic effects of the naphthyl groups.

中文翻译:

自由基阳离子中间体的开环速率控制1和2-萘基取代的亚甲基环丙烷在热致发光方面的差异

在这项研究中,我们观察到亚甲基环丙烷1 c在三元环的C-2处具有双苯基和1-萘基,它们在低温矩阵中发射绿色热致发光(TL),与480中的两组谱带相关–600和600–700 nm区域。这些波段分别对应于相应的三亚甲基双自由基3 2 c .. *的3 1 c *和三重态三重态(TT)荧光(FL)发出的磷光。相反,如先前报道,类似的2-萘基衍生物1b发出红色TL,与350-450和600-700 nm区域中的两个谱带相关,这两个谱带从1 1 b *分配给FL,从T 1 FL分配给T-T FL3 2 b .. *。光谱研究和密度泛函理论计算的结果表明,在1b1c的TL特性中观察到的差异是与立体电子相关的1b 。+1c 。+的亚甲基环丙烷开环速率不同的结果萘基的影响。
更新日期:2019-10-23
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