The Raman fingerprint of cyclic conjugation: the case of the stabilization of cations and dications in cycloparaphenylenes

Chemical Science
Miriam Peña AlvarezJuan Casado

Abstract

Radical cations and dications of [n]CPP from n = 5 to n = 12 have been studied by Raman spectroscopy and density functional theory. Small [n]CPP dications owe their stability to the closed-shell electronic structure imposed by cyclic conjugation surpassing the destabilizing effect of ring strain and of the electron deficiency of the charged states. Large [n]CPP dications mitigate cyclic strain by forming diradicals. The Raman spectra reflect the balance among cyclic conjugation, cyclic strain and biradicaloid stabilization by finding an unexpected turning point in the frequency behavior of the G vibrational modes as a function of size. These Raman data represent the vibrational fingerprint of this rare form of conjugation which is central to stabilize both cations and dications of [n]CPP macrocycles.

References

Jul 30, 1999·Angewandte Chemie·H S Choi, K S Kim
Nov 17, 2001·Chemical Reviews·T M Krygowski, M K Cyrański
Aug 19, 2004·Angewandte Chemie·Takeshi Kawase, Masaji Oda
Dec 15, 2006·Chemical Reviews·Rainer Herges
Dec 6, 2008·Journal of the American Chemical Society·Ramesh JastiCarolyn R Bertozzi
Apr 21, 2010·Organic Letters·Yasutomo SegawaKenichiro Itami
May 6, 2011·Journal of the American Chemical Society·Takahiro IwamotoShigeru Yamago
Sep 15, 2011·Journal of the American Chemical Society·Thomas J SistoRamesh Jasti
Nov 5, 2011·Organic Letters·Elizabeth S HirstRamesh Jasti
Jan 31, 2012·Angewandte Chemie·Jianlong Xia, Ramesh Jasti
Jun 22, 2013·Nature Chemistry·Haruka OmachiKenichiro Itami
Nov 21, 2013·Angewandte Chemie·Eiichi KayaharaShigeru Yamago
Jan 17, 2014·Journal of the American Chemical Society·Masahiko IyodaYoshito Tobe
Jan 24, 2014·Angewandte Chemie·Florian E GollingKlaus Müllen
Jan 28, 2014·Journal of the American Chemical Society·Eiichi KayaharaShigeru Yamago
Dec 20, 2014·Journal of the American Chemical Society·Naoyuki ToriumiMasanobu Uchiyama

❮ Previous
Next ❯

Citations

Sep 29, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Miriam Peña-ÁlvarezMargherita Citroni
Sep 13, 2017·Chemistry : a European Journal·Lili QiuMiklos Kertesz
Jan 15, 2019·Physical Chemistry Chemical Physics : PCCP·Sofia CanolaFabrizia Negri
Jun 28, 2018·Chemical Communications : Chem Comm·Sarah N SpisakMarina A Petrukhina
Mar 30, 2021·Chemistry : a European Journal·Saber MirzaeiRaúl Hernández Sánchez
Apr 19, 2019·Journal of the American Chemical Society·Kabali SenthilkumarMarcin Stępień
May 23, 2018·Journal of the American Chemical Society·Xian-Sheng KeJonathan L Sessler
Jan 12, 2021·The Journal of Physical Chemistry. a·Rabia AyubHenrik Ottosson

❮ Previous
Next ❯

Software Mentioned

Gaussian

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.