Benzo-thia-fused [n ]thienoacenequinodimethanes with small to moderate diradical characters: the role of pro-aromaticity versus anti-aromaticity

Chemical Science
Xueliang ShiChunyan Chi

Abstract

Open-shell singlet diradicaloids have recently received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing design. However, the need for a fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties remains unaddressed. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n = 1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n = 1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-phot...Continue Reading

References

May 14, 2004·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Juan CasadoJuan T López Navarrete
Jun 23, 2005·Journal of the American Chemical Society·Toshiaki TakahashiYoshio Aso
Jul 28, 2005·Journal of the American Chemical Society·Xinnan ZhangAdam J Matzger
Jul 15, 2006·The Journal of Physical Chemistry. a·Masayoshi NakanoKizashi Yamaguchi
Nov 30, 2007·Angewandte Chemie·John E Anthony
Jun 24, 2009·Angewandte Chemie·Akihiro ShimizuTakashi Kubo
Oct 8, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Reyes Malavé OsunaAdam J Matzger
Nov 26, 2009·Chemistry : a European Journal·Rocío Ponce OrtizTetsuo Otsubo
Aug 18, 2010·Angewandte Chemie·Tsun-Cheng WuYao-Ting Wu
Sep 25, 2010·Organic Letters·Zhe SunJishan Wu
Jan 27, 2011·Angewandte Chemie·Daniel T ChaseMichael M Haley
Feb 11, 2011·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Juan Casado, Juan T López Navarrete
Apr 14, 2011·The Journal of Organic Chemistry·Tae-Hyuk KwonAndrew B Holmes
Jun 17, 2011·Angewandte Chemie·Akihiro Shimizu, Yoshito Tobe
Jul 16, 2011·Journal of the American Chemical Society·Zhe SunJishan Wu
Aug 16, 2011·Advanced Materials·Kazuo TakimiyaEigo Miyazaki
Sep 22, 2011·Journal of the American Chemical Society·Xiaozhang ZhuEiichi Nakamura
Apr 27, 2012·Organic Letters·Bradley D RoseMichael M Haley
Jul 19, 2012·Chemical Society Reviews·Juan CasadoJuan T López Navarrete
Aug 23, 2012·Journal of the American Chemical Society·Yuan LiJishan Wu
Oct 24, 2012·Journal of the American Chemical Society·Eleonora V CanesiChiara Castiglioni
Oct 26, 2012·Topics in Current Chemistry·Aaron G FixMichael M Haley
Mar 7, 2013·Organic Letters·Aaron G FixMichael M Haley
Jul 17, 2013·Chemistry, an Asian Journal·Zhe SunJishan Wu
Jul 26, 2013·Chemical Reviews·Manabu Abe
Oct 24, 2013·Chemistry : a European Journal·Wangdong ZengJishan Wu
Apr 15, 2014·Chemical Science·Brian S YoungMichael M Haley
Jul 30, 2014·Accounts of Chemical Research·Zhe SunJishan Wu
Oct 28, 2014·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Takashi Kubo
Dec 20, 2014·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Zebing Zeng, Jishan Wu

❮ Previous
Next ❯

Citations

Feb 6, 2018·Chemistry : a European Journal·Wangdong ZengJishan Wu
Dec 23, 2017·Chemistry, an Asian Journal·Mariusz TasiorDaniel T Gryko
Jun 1, 2017·Chemistry, an Asian Journal·Yi LiuJishan Wu
Jan 13, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sangsu LeeDongho Kim
Jun 22, 2017·Topics in Current Chemistry·Xueliang Shi, Chunyan Chi
Nov 13, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Ya-Ping OuSheng Hua Liu
Jul 19, 2016·The Journal of Organic Chemistry·Mariusz Tasior, Daniel T Gryko
Aug 26, 2017·Journal of the American Chemical Society·Xuefeng LuJishan Wu
Dec 7, 2018·Journal of the American Chemical Society·Yuta OkamotoMasanobu Uchiyama

❮ Previous
Next ❯

Methods Mentioned

BETA
acylation
X-ray
NMR
ESR

Software Mentioned

TIPS
BDTh

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.