Planarization, fusion, and strain of carbon-bridged phenylenevinylene oligomers enhance π-electron and charge conjugation: a dissectional vibrational Raman study

Journal of the American Chemical Society
Paula Mayorga BurrezoJuan Casado

Abstract

We have used Raman spectroscopy to study the molecular and electronic structures of the radical cations and dications of carbon-bridged oligo(para-phenylenevinylene)s (COPVn, n = 1-6) possessing consecutive fused pentagons and hexagons, up to 19, along with COPV derivatives having electron-donating and -withdrawing groups. This study was made possible by the outstanding stability of the charged states of COPVs. We could untangle the effects of π-conjugation in the planar structure on the Raman frequency by distinguishing it from other structural effects, such as strain in the vinylene groups shared by the two pentagons. The analyses showed that the radical cations have benzo-quinoidal structures confined in the center of the molecule, as well as benzo-aromatic rings at the terminal sites. In contrast, dications of COPVn longer than n = 3 exhibit a biradicaloid character because of the recovery of aromaticity in the central rings and quinoidal rings at the terminal positions. These biradicaloids favor a singlet nature in their ground electronic states because of the double spin polarization. The introduction of electron-donating and -withdrawing groups on the termini of a COPV core affords, upon oxidation or reduction, a fully d...Continue Reading

References

Jul 15, 1987·Physical Review. B, Condensed Matter·E EhrenfreundB Horovitz
Nov 6, 2003·Journal of the American Chemical Society·Shigehiro YamaguchiKohei Tamao
Jan 7, 2005·Chemistry : a European Journal·Gema de la TorreDirk M Guldi
Feb 11, 2005·Journal of the American Chemical Society·Caihong XuShigehiro Yamaguchi
Jun 17, 2008·Science·Seong Ho ChoiC Daniel Frisbie
Jun 24, 2009·Angewandte Chemie·Akihiro ShimizuTakashi Kubo
Sep 5, 2009·Journal of the American Chemical Society·Xiaozhang ZhuEiichi Nakamura
Apr 17, 2010·Chemical Society Reviews·Hagen Klauk
Aug 12, 2010·Journal of the American Chemical Society·Akihito KonishiTakashi Kubo
Aug 18, 2010·Angewandte Chemie·Tsun-Cheng WuYao-Ting Wu
Mar 31, 2011·Journal of the American Chemical Society·Vega LloverasJaume Veciana
May 18, 2011·Chemical Reviews·Jihane Hankache, Oliver S Wenger
Jun 17, 2011·Angewandte Chemie·Akihiro Shimizu, Yoshito Tobe
Sep 22, 2011·Journal of the American Chemical Society·Sandra R GonzálezJuan Casado
Sep 22, 2011·Journal of the American Chemical Society·Xiaozhang ZhuEiichi Nakamura
Nov 19, 2011·Angewandte Chemie·Alexander Heckmann, Christoph Lambert
Oct 31, 2012·Journal of the American Chemical Society·Xiaozhang ZhuEiichi Nakamura
May 18, 2013·Journal of the American Chemical Society·Mateusz WielopolskiNazario Martín
Jul 26, 2013·Chemical Reviews·Manabu Abe
Jul 30, 2014·Accounts of Chemical Research·Zhe SunJishan Wu
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes

❮ Previous
Next ❯

Citations

Aug 6, 2016·Journal of the American Chemical Society·Qifan YanEiichi Nakamura
Jul 28, 2015·Physical Chemistry Chemical Physics : PCCP·K D ThériaultT C Sutherland
Dec 15, 2017·Chemistry : a European Journal·Paula Mayorga BurrezoJuan Casado
Mar 24, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Samara Medina RiveroJuan Casado
Oct 10, 2018·Chemistry : a European Journal·Masami ItoKosuke Namba
Jan 19, 2019·Chemistry, an Asian Journal·Hayato TsujiEiichi Nakamura
Jun 4, 2019·The Journal of Chemical Physics·María E Sandoval-SalinasDavid Casanova
Nov 19, 2020·Journal of the American Chemical Society·Hideki HayashiJuan Casado
Sep 17, 2019·Accounts of Chemical Research·Hayato Tsuji, Eiichi Nakamura
Dec 31, 2016·The Journal of Organic Chemistry·Koichi MurayamaKen Tanaka
Oct 23, 2020·Journal of the American Chemical Society·Hua LuEiichi Nakamura

❮ Previous
Next ❯

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.