Outer-sphere effects on ligand-field excited-state dynamics: solvent dependence of high-spin to low-spin conversion in [Fe(bpy)3]2.

Chemical Science
Jennifer N Miller, James K McCusker

Abstract

In condensed phase chemistry, the solvent can have a significant impact on everything from yield to product distribution to mechanism. With regard to photo-induced processes, solvent effects have been well-documented for charge-transfer states wherein the redistribution of charge subsequent to light absorption couples intramolecular dynamics to the local environment of the chromophore. Ligand-field excited states are expected to be largely insensitive to such perturbations given that their electronic rearrangements are localized on the metal center and are therefore insulated from so-called outer-sphere effects by the ligands themselves. In contrast to this expectation, we document herein a nearly two-fold variation in the time constant associated with the 5T2 → 1A1 high-spin to low-spin relaxation process of tris(2,2'-bipyridine)iron(ii) ([Fe(bpy)3]2+) across a range of different solvents. Likely origins for this solvent dependence, including relevant solvent properties, ion pairing, and changes in solvation energy, were considered and assessed by studying [Fe(bpy)3]2+ and related derivatives via ultrafast time-resolved absorption spectroscopy and computational analyses. It was concluded that the effect is most likely associat...Continue Reading

References

Feb 19, 2002·Chemical Reviews·Pingyun Chen, Thomas J. Meyer
Apr 1, 2003·Journal of Computational Chemistry·Maurizio CossiVincenzo Barone
May 5, 2005·Journal of the American Chemical Society·Eric A Juban, James K McCusker
Jan 6, 2006·The Journal of Physical Chemistry. a·Munira KhalilRobert W Schoenlein
Oct 10, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Ilia A Guzei, Mark Wendt
Nov 10, 2006·Chemical Reviews·Yizhak Marcus, Glenn Hefter
Jun 2, 2007·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·J R MannekutlaS R Inamdar
Jul 24, 2015·Nature Chemistry·Gerald Auböck, Majed Chergui
Dec 15, 2015·The Journal of Physical Chemistry. B·Akshaya Kumar DasMarkus Meuwly
Jan 20, 2016·The Journal of Physical Chemistry. B·Kristoffer HaldrupChristian Bressler
Feb 16, 2016·The Journal of Physical Chemistry. B·Junming Ho, Mehmed Z Ertem
Apr 7, 2016·Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials·Colin R GroomSuzanna C Ward
Jan 8, 2019·Chemistry : a European Journal·Oliver S Wenger
Feb 7, 2020·Chemical Society Reviews·Christoph Förster, Katja Heinze

❮ Previous
Next ❯

Citations


❮ Previous
Next ❯

Methods Mentioned

BETA
nuclear magnetic resonance
X-ray

Software Mentioned

ECAKUP
MEMSON
ADEJOK
Gaussian
Igor Pro
NUZKOI

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.