Intramolecular charge transfer with the planarized 4-cyanofluorazene and its flexible counterpart 4-cyano-N-phenylpyrrole. Picosecond fluorescence decays and femtosecond excited-state absorption

The Journal of Physical Chemistry. a
Sergey I DruzhininKlaas A Zachariasse

Abstract

The fluorescence spectrum of the rigidified 4-cyanofluorazene (FPP4C) in n-hexane consists of a dual emission from a locally excited (LE) and an intramolecular charge-transfer (ICT) state, with an ICT/LE fluorescence quantum yield ratio of Phi'(ICT)/Phi(LE) = 3.3 at 25 degrees C. With the flexible 4-cyano- N-phenylpyrrole (PP4C) in n-hexane, such an ICT reaction also takes place, with Phi'(ICT)/Phi(LE) = 1.5, indicating that for this reaction, a perpendicular twist of the pyrrole and benzonitrile moieties is not required. The ICT emission band of FPP4C and PP4C in n-hexane has vibrational structure, but a structureless band is observed in all other solvents more polar than the alkanes. The enthalpy difference Delta H of the LE --> ICT reaction in n-hexane, -11 kJ/mol for FPP4C and -7 kJ/mol for PP4C, is determined by analyzing the temperature dependence of Phi'(ICT)/Phi(LE). Using these data, the energy E(FC,ICT) of the Franck-Condon ground state populated by the ICT emission is calculated, 41 (FPP4C) and 40 kJ/mol (PP4C). These large values for E(FC,ICT) lead to the conclusion that with FPP4C and PP4C, direct ICT excitation, bypassing LE, does not take place. FPP4C has an ICT dipole moment of 15 D, similar to that of PP4C (16 ...Continue Reading

References

Apr 26, 2003·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Toshitada YoshiharaKlaas A Zachariasse
Feb 12, 2004·Journal of the American Chemical Society·Klaas A ZachariasseReinhard Machinek
Jul 9, 2004·Journal of the American Chemical Society·Toshitada YoshiharaKlaas A Zachariasse
Nov 8, 2005·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Victor A GalievskyKlaas A Zachariasse
Jan 6, 2006·The Journal of Physical Chemistry. a·Sukumaran Murali, Wolfgang Rettig
Mar 3, 2006·The Journal of Physical Chemistry. a·Sergey I DruzhininKlaas A Zachariasse
Mar 9, 2006·Journal of the American Chemical Society·Semyon CoganYehuda Haas
Mar 11, 2006·The Journal of Physical Chemistry. a·Sergei ArzhantsevMark Maroncelli
Jul 13, 2006·The Journal of Physical Chemistry. a·Toshitada YoshiharaKlaas A Zachariasse
Jul 13, 2006·The Journal of Physical Chemistry. a·Sukumaran MuraliA V Kropachev
Jul 13, 2006·The Journal of Physical Chemistry. a·Yoshiaki Amatatsu
Dec 7, 2006·Journal of the American Chemical Society·Christof HättigAndreas Köhn
Apr 10, 2007·Journal of the American Chemical Society·J L Pérez-LustresS A Kovalenko
Aug 7, 2007·Physical Review Letters·M BraunM Woerner
Oct 13, 2007·The Journal of Physical Chemistry. a·Venugopal KarunakaranNikolaus P Ernsting
Jan 26, 2008·The Journal of Physical Chemistry. a·Attila Demeter, Klaas A Zachariasse

❮ Previous
Next ❯

Citations

Feb 11, 2014·Journal of Fluorescence·Jayanta K Nath, Jubaraj B Baruah
Dec 8, 2015·The Journal of Physical Chemistry. a·Mercedes Vanessa BohnwagnerAndreas Dreuw
Feb 7, 2013·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Benedetta CarlottiFausto Elisei
Jun 6, 2014·Physical Chemistry Chemical Physics : PCCP·Benedetta CarlottiVincenzo Barone
Aug 14, 2009·The Journal of Physical Chemistry. a·Kathrin MeindlDietmar Stalke
Sep 2, 2009·The Journal of Physical Chemistry. a·Sergey I DruzhininKlaas A Zachariasse
Jan 2, 2010·The Journal of Physical Chemistry. a·Sergey I DruzhininKlaas A Zachariasse
Aug 13, 2010·The Journal of Physical Chemistry. a·Lixin XiaoXingzhong Yan
Nov 13, 2010·The Journal of Physical Chemistry. a·Victor A GalievskyKlaas A Zachariasse
Feb 15, 2011·The Journal of Physical Chemistry. a·Attila DemeterKlaas A Zachariasse
Jul 21, 2017·The Journal of Physical Chemistry. a·Mercedes Vanessa Bohnwagner, Andreas Dreuw
Jul 12, 2019·The Journal of Physical Chemistry. a·Michał Andrzej Kochman, Bo Durbeej

❮ 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.