Light Activation and Photophysics of a Structurally Constrained Nickel(II)-Bipyridine Aryl Halide Complex
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00583883" target="_blank" >RIV/61388963:_____/24:00583883 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1021/acs.inorgchem.3c03822" target="_blank" >https://doi.org/10.1021/acs.inorgchem.3c03822</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.3c03822" target="_blank" >10.1021/acs.inorgchem.3c03822</a>
Alternative languages
Result language
angličtina
Original language name
Light Activation and Photophysics of a Structurally Constrained Nickel(II)-Bipyridine Aryl Halide Complex
Original language description
Transition-metal photoredox catalysis has transformed organic synthesis by harnessing light to construct complex molecules. Nickel(II)-bipyridine (bpy) aryl halide complexes are a significant class of cross-coupling catalysts that can be activated via direct light excitation. This study investigates the effects of molecular structure on the photophysics of these catalysts by considering an underexplored, structurally constrained Ni(II)-bpy aryl halide complex in which the aryl and bpy ligands are covalently tethered alongside traditional unconstrained complexes. Intriguingly, the tethered complex is photochemically stable but features a reversible Ni(II)-C(aryl)><- [Ni(I)<middle dot><middle dot><middle dot>C(aryl)(center dot)] equilibrium upon direct photoexcitation. When an electrophile is introduced during photoirradiation, we demonstrate a preference for photodissociation over recombination, rendering the parent Ni(II) complex a stable source of a reactive Ni(I) intermediate. Here, we characterize the reversible photochemical behavior of the tethered complex by kinetic analyses, quantum chemical calculations, and ultrafast transient absorption spectroscopy. Comparison to the previously characterized Ni(II)-bpy aryl halide complex indicates that the structural constraints considered here dramatically influence the excited state relaxation pathway and provide insight into the characteristics of excited-state Ni(II)-C bond homolysis and aryl radical reassociation dynamics. This study enriches the understanding of molecular structure effects in photoredox catalysis and offers new possibilities for designing customized photoactive catalysts for precise organic synthesis.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
63
Issue of the periodical within the volume
9
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
4120-4131
UT code for WoS article
001167956000001
EID of the result in the Scopus database
2-s2.0-85186253956