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Title: X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives

Abstract

A combination of Cr K-edge XAS and DFT calculations have been performed on archetypal chromium porphyrinoid complexes CrIV[TMP]O (2) and CrV[TPC]O (3), and the results have been compared to the reference compound CrIII[TPP]Cl (1), where TPP2–, TMP2–, and TPC3– are the anions of meso-tetraphenylporphyrin, meso-tetramesitylporphyrin, and meso-triphenylcorrole, respectively. The intensity-weighted average energy position in 1 (5990.9 eV), 2 (5992.0 eV) and 3 (5992.6 eV) are consistent with increasing the metal oxidation state along the series. EXAFS and theoretical analysis of 2 and 3 reveal that the Cr–O bond is longer and weaker in 3 relative to 2, despite the structural similarity and increase in oxidation state in 3. This is also reflected in a comparison of the Cr K-pre-edge transitions. The roughly twenty-fold increase in intensity in the two oxo complexes is unsurprising and well-precedented for other first-row transition metals. However, although 3 had greater overall intensity, the intensity of transitions along the Cr–O bond is greater. EXAFS, DFT and TDDFT analyses show that the more contracted N4 core of the corrole results in a greater out-of-plane displacement of the Cr in 3 relative to 2, which in turn accentuates the lower local symmetry of the Cr in 3 relativemore » to 2. This difference helps us to appreciate the TDDFT result that whereas two 1s→ 3dz2 transitions make up the majority of the intensity in the pre-edge of 2, the pre-edge of 3 also includes fairly intense transitions to molecular orbitals with 3dxz, 3dyz and 3dz2 character, thus accounting for the somewhat higher overall intensity for 3.« less

Authors:
 [1];  [2]; ORCiD logo [2];  [1]
  1. Stanford Synchrotron Radiation Lightsource;SLAC National Accelerator Laboratory;Stanford University;Menlo Park;USA
  2. Department of Chemistry;UiT – the Arctic University of Norway;N-9037 Tromsø;Norway
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Org.:
USDOE Office of Science (SC); Research Council of Norway; National Institutes of Health (NIH)
OSTI Identifier:
1631193
Alternate Identifier(s):
OSTI ID: 1647632
Grant/Contract Number:  
AC02-76SF00515; 262229; P41GM103393
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 10 Journal Issue: 35; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cao, Rui, Thomas, Kolle E., Ghosh, Abhik, and Sarangi, Ritimukta. X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/d0ra02335c.
Cao, Rui, Thomas, Kolle E., Ghosh, Abhik, & Sarangi, Ritimukta. X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives. United Kingdom. https://doi.org/10.1039/d0ra02335c
Cao, Rui, Thomas, Kolle E., Ghosh, Abhik, and Sarangi, Ritimukta. Wed . "X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives". United Kingdom. https://doi.org/10.1039/d0ra02335c.
@article{osti_1631193,
title = {X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives},
author = {Cao, Rui and Thomas, Kolle E. and Ghosh, Abhik and Sarangi, Ritimukta},
abstractNote = {A combination of Cr K-edge XAS and DFT calculations have been performed on archetypal chromium porphyrinoid complexes CrIV[TMP]O (2) and CrV[TPC]O (3), and the results have been compared to the reference compound CrIII[TPP]Cl (1), where TPP2–, TMP2–, and TPC3– are the anions of meso-tetraphenylporphyrin, meso-tetramesitylporphyrin, and meso-triphenylcorrole, respectively. The intensity-weighted average energy position in 1 (5990.9 eV), 2 (5992.0 eV) and 3 (5992.6 eV) are consistent with increasing the metal oxidation state along the series. EXAFS and theoretical analysis of 2 and 3 reveal that the Cr–O bond is longer and weaker in 3 relative to 2, despite the structural similarity and increase in oxidation state in 3. This is also reflected in a comparison of the Cr K-pre-edge transitions. The roughly twenty-fold increase in intensity in the two oxo complexes is unsurprising and well-precedented for other first-row transition metals. However, although 3 had greater overall intensity, the intensity of transitions along the Cr–O bond is greater. EXAFS, DFT and TDDFT analyses show that the more contracted N4 core of the corrole results in a greater out-of-plane displacement of the Cr in 3 relative to 2, which in turn accentuates the lower local symmetry of the Cr in 3 relative to 2. This difference helps us to appreciate the TDDFT result that whereas two 1s→ 3dz2 transitions make up the majority of the intensity in the pre-edge of 2, the pre-edge of 3 also includes fairly intense transitions to molecular orbitals with 3dxz, 3dyz and 3dz2 character, thus accounting for the somewhat higher overall intensity for 3.},
doi = {10.1039/d0ra02335c},
journal = {RSC Advances},
number = 35,
volume = 10,
place = {United Kingdom},
year = {2020},
month = {1}
}

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