Cyclopenta[b]naphthalene cyanoacrylate dyes: synthesis and evaluation as fluorescent molecular rotors.
Cyclopenta[b]naphthalene cyanoacrylate dyes: synthesis and evaluation as fluorescent molecular rotors.
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DOI：
10.1039/c4ob02563f
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发表时间：
2015-03-14
影响因子：
3.2
通讯作者：
Theodorakis EA
中科院分区：
文献类型：
--
作者：
Kocsis LS;Elbel KM;Hardigree BA;Brummond KM;Haidekker MA;Theodorakis EA
我们描述了一个家庭的环境敏感性染料的设计，合成和荧光概况，其中二甲氨基（供体）基团共轭氰基丙烯酸酯（受体）单元通过环戊二烯并[B]萘环系统。该组装体满足荧光分子转子的典型D-π-A基序，并表现出溶剂化变色和粘度敏感的荧光发射。这些染料的中心萘环系统是通过一种新的分子内双脱氢-狄尔斯-桤木（IDDDA）反应，允许在芳香核周围的可变位置的供体和受体基团的掺入合成的。一个红移的激发和发射峰观察到溶剂极性的增加，但染料表现出复杂的发射模式与第二个红色发射带时，溶解在非极性溶剂。与其他已知的分子转子一致，发射强度随着粘度的增加而增加。有趣的是，供体和受体基团之间更紧密的空间接近导致粘度敏感性降低，同时量子产率增加。这一观察结果表明，当供体和受体基团非常接近时，分子内旋转的结构阻碍占主导地位。所检查的化合物提供洞察如何激发态分子内旋转可以同时受到溶剂和化学结构的影响。
We describe the design, synthesis and fluorescent profile of a family of environment-sensitive dyes in which a dimethylamino (donor) group is conjugated to a cyanoacrylate (acceptor) unit via a cyclopenta[b]naphthalene ring system. This assembly satisfies the typical D-π-A motif of a fluorescent molecular rotor and exhibits solvatochromic and viscosity-sensitive fluorescence emission. The central naphthalene ring system of these dyes was synthesized via a novel intramolecular dehydrogenative dehydro-Diels-Alder (IDDDA) reaction that permits incorporation of the donor and acceptor groups in variable positions around the aromatic core. A bathochromic shift of excitation and emission peaks was observed with increasing solvent polarity but the dyes exhibited a complex emission pattern with a second red emission band when dissolved in nonpolar solvents. Consistent with other known molecular rotors, the emission intensity increased with increasing viscosity. Interestingly, closer spatial proximity between the donor and the acceptor groups led to decreased viscosity sensitivity combined with an increased quantum yield. This observation indicates that structural hindrance of intramolecular rotation dominates when the donor and acceptor groups are in close proximity. The examined compounds give insight into how excited state intramolecular rotation can be influenced by both the solvent and the chemical structure.
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影响因子：
5.6
作者：
Haidekker MA;Theodorakis EA
通讯作者：
Theodorakis EA
影响因子：
--
作者：
Haidekker, Mark A.;Lichlyter, Darcy;Grimes, Craig A.
通讯作者：
Grimes, Craig A.
影响因子：
3.1
作者：
Abelt, Christopher J.;Sun, Tao;Everett, Renata K.
通讯作者：
Everett, Renata K.
影响因子：
62.1
作者：
Kobayashi, Hisataka;Ogawa, Mikako;Alford, Raphael;Choyke, Peter L.;Urano, Yasuteru
通讯作者：
Urano, Yasuteru
影响因子：
3.2
作者：
Haidekker, Mark A.;Theodorakis, Emmanuel A.
通讯作者：
Theodorakis, Emmanuel A.