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Title: Site-specific electronic structure of covalently linked bimetallic dyads from nitrogen K-edge x-ray absorption spectroscopy

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0192809 · OSTI ID:2315040
ORCiD logo [1];  [2];  [3];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [5];  [6]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [3]
  1. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); SLAC National Accelerator Laboratory
  2. University of Washington, Seattle, WA (United States)
  3. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)
  4. Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  5. Ulm University (Germany)
  6. Leibniz Institute of Photonic Technology, Jena (Germany); Friedrich Schiller University, Jena (Germany)
+ Show Author Affiliations

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. Here these results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); German Research Foundation (DFG)
Grant/Contract Number:
AC02-76SF00515; AC02-06CH11357; AC02-05CH11231
OSTI ID:
2315040
Alternate ID(s):
OSTI ID: 2499797
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 160; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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