Rates of Ring Opening of Radical Cation Intermediates Govern Differences in Thermoluminescence between 1‐ and 2‐Naphthyl‐Substituted Methylenecyclopropanes,ChemPhotoChem

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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³2 c ^.. *的³1 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¹1 b *分配给FL，从T 1 FL分配给T-T FL³2 b ^.. *。光谱研究和密度泛函理论计算的结果表明，在1b和1c的TL特性中观察到的差异是与立体电子相关的1b ^。+和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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