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刚性5,10-二氢茚并[2,1-]茚与2,2'-二烷氧基-1,1'-联萘共轭物及共聚物的圆偏振发光和高光致发光量子产率

Circularly polarized luminescence and high photoluminescence quantum yields from rigid 5,10-dihydroindeno[2,1-]indene and 2,2'-dialkoxy-1,1'-binaphthyl conjugates and copolymers.

作者信息

Iwata Keisuke, Tsurui Makoto, Itaya Kosuke, Hamaguchi Naoto, Egawa Yasunobu, Kitagawa Yuichi, Hasegawa Yasuchika, Tsuji Hayato

机构信息

Department of Chemistry, Faculty of Science, Kanagawa University 3-27-1 Rokkaku-bashi, Kanagawa-ku Yokohama 221-8686 Japan

Faculty of Engineering, Hokkaido University Kita13 Nishi8, Kita-ku Sapporo 060-8628 Japan.

出版信息

RSC Adv. 2024 Feb 29;14(11):7251-7257. doi: 10.1039/d4ra00380b.

DOI:10.1039/d4ra00380b
PMID:38433937
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10902698/
Abstract

5,5,10,10-Tetramethyl-5,10-dihydroindeno[2,1-]indene (COPV1(Me)) was installed into either the 3,3'- or 6,6'-positions of chiral 2,2'-dioctyloxy-1,1'-binaphthyl to afford 2 : 1 conjugates (monomeric compounds) and 1 : 1 copolymers. These compounds showed high photoluminescence quantum yields of >0.95 whilst also exhibiting circular dichroism (CD) and circularly polarized luminescence (CPL). The dissymmetry factors of CPL () for the 3,3'- and 6,6'-monomeric compounds in THF were 6.6 × 10 and 3.3 × 10, respectively. The 3,3'-isomer has a higher value than the 6,6'-isomer, which was attributed to the difference in the extent of π-conjugation and the angle between electronic and magnetic transition moments. The values of the 3,3'-linked and 6,6'-linked copolymers were 1.1 × 10 and 6.8 × 10, respectively. The structural rigidity of the COPV units is beneficial to achieve relatively high values whilst maintaining a photoluminescence quantum yield that is close to unity by using a single type of fluorophore.

摘要

将5,5,10,10-四甲基-5,10-二氢茚并[2,1-]茚(COPV1(Me))安装到手性2,2'-二辛氧基-1,1'-联萘的3,3'-或6,6'-位上,得到2∶1的共轭物(单体化合物)和1∶1的共聚物。这些化合物显示出大于0.95的高光致发光量子产率,同时还表现出圆二色性(CD)和圆偏振发光(CPL)。在四氢呋喃中,3,3'-和6,6'-单体化合物的圆偏振发光不对称因子()分别为6.6×10和3.3×10。3,3'-异构体的值高于6,6'-异构体,这归因于π共轭程度以及电子和磁跃迁矩之间角度的差异。3,3'-连接和6,6'-连接的共聚物的值分别为1.1×10和6.8×10。通过使用单一类型的荧光团,COPV单元的结构刚性有利于实现相对较高的值,同时保持接近1的光致发光量子产率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/57fe8a4a9327/d4ra00380b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/cef8150eb2b5/d4ra00380b-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/f0a1d5a4544b/d4ra00380b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/57fe8a4a9327/d4ra00380b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/cef8150eb2b5/d4ra00380b-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/f0a1d5a4544b/d4ra00380b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/209c/10902698/57fe8a4a9327/d4ra00380b-f2.jpg

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本文引用的文献

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Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness.
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Chemistry. 2022 Oct 21;28(59):e202202218. doi: 10.1002/chem.202202218. Epub 2022 Sep 29.
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J Am Chem Soc. 2022 Jun 29;144(25):11397-11404. doi: 10.1021/jacs.2c04012. Epub 2022 Jun 17.
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