Sökning: WFRF:(Gaffney Kelly J.)
> (2020-2023) >
Quantifying the Ste...
Quantifying the Steric Effect on Metal-Ligand Bonding in Fe Carbene Photosensitizers with Fe 2p3d Resonant Inelastic X-ray Scattering
-
- Kunnus, Kristjan (författare)
- University of Tartu,Stanford Linear Accelerator Center (SLAC)
-
- Guo, Meiyuan (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
-
- Biasin, Elisa (författare)
- Stanford Linear Accelerator Center (SLAC)
-
visa fler...
-
- Larsen, Christopher B. (författare)
- Stanford Linear Accelerator Center (SLAC)
-
- Titus, Charles J. (författare)
- Stanford University
-
- Lee, Sang Jun (författare)
- Stanford Linear Accelerator Center (SLAC)
-
- Nordlund, Dennis (författare)
- Stanford Linear Accelerator Center (SLAC)
-
- Cordones, Amy A. (författare)
- Stanford Linear Accelerator Center (SLAC)
-
- Uhlig, Jens (författare)
- Lund University,Lunds universitet,NanoLund: Centre for Nanoscience,Annan verksamhet, LTH,Lunds Tekniska Högskola,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Other operations, LTH,Faculty of Engineering, LTH,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
-
- Gaffney, Kelly J. (författare)
- Stanford Linear Accelerator Center (SLAC)
-
visa färre...
-
(creator_code:org_t)
- 2022-01-14
- 2022
- Engelska.
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 61:4, s. 1961-1972
- Relaterad länk:
-
http://dx.doi.org/10...
-
visa fler...
-
https://lup.lub.lu.s...
-
https://doi.org/10.1...
-
visa färre...
Abstract
Ämnesord
Stäng
- Understanding the electronic structure and chemical bonding of transition metal complexes is important for improving the function of molecular photosensitizers and catalysts. We have utilized X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L3 edge to investigate the electronic structure of two Fe N-heterocyclic carbene complexes with similar chemical structures but different steric effects and contrasting excited-state dynamics: [Fe(bmip)2]2+ and [Fe(btbip)2]2+, bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)pyridine and btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine. In combination with charge transfer multiplet and ab initio calculations, we quantified how changes in Fe-carbene bond length due to steric effects modify the metal-ligand bonding, including σ/πdonation and πback-donation. We find that σ donation is significantly stronger in [Fe(bmip)2]2+, whereas the πback-donation is similar in both complexes. The resulting stronger ligand field and nephelauxetic effect in [Fe(bmip)2]2+ lead to approximately 1 eV destabilization of the quintet metal-centered 5T2g excited state compared to [Fe(btbip)2]2+, providing an explanation for the absence of a photoinduced 5T2g population and a longer metal-to-ligand charge-transfer excited-state lifetime in [Fe(bmip)2]2+. This work demonstrates how combined modeling of XAS and RIXS spectra can be utilized to understand the electronic structure of transition metal complexes governed by correlated electrons and donation/back-donation interactions.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
Publikations- och innehållstyp
- art (ämneskategori)
- ref (ämneskategori)
Hitta via bibliotek
Till lärosätets databas
- Av författaren/redakt...
-
Kunnus, Kristjan
-
Guo, Meiyuan
-
Biasin, Elisa
-
Larsen, Christop ...
-
Titus, Charles J ...
-
Lee, Sang Jun
-
visa fler...
-
Nordlund, Dennis
-
Cordones, Amy A.
-
Uhlig, Jens
-
Gaffney, Kelly J ...
-
visa färre...
- Om ämnet
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Kemi
-
och Fysikalisk kemi
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Fysik
-
och Atom och molekyl ...
- Artiklar i publikationen
-
Inorganic Chemis ...
- Av lärosätet
-
Lunds universitet