We report the isolation and characterization of a series of trinickel complexes with 2,3,6,7,10,11‐hexaoxytriphenylene (HOTP), [(Me3TPANi)3(HOTP)](BF4)
We report the isolation and characterization of a series of trinickel complexes with 2,3,6,7,10,11‐hexaoxytriphenylene (HOTP), [(Me3TPANi)3(HOTP)](BF4)
- NSF-PAR ID:
- 10308304
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 60
- Issue:
- 44
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 23784-23789
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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1 ), which has a formal Cu(III) oxidation state but whose physical analysis has led some to a Cu(I) assignment in an inverted ligand field model. Recent examinations of1 by X‐ray spectroscopies have led previous authors to contradictory conclusions, motivating the re‐examination of its X‐ray absorption profile here by a complementary method, resonant diffraction anomalous fine structure (DAFS). From analysis of DAFS measurements for a series of seven mononuclear Cu complexes including1 , here it is shown that there is a systematic trifluoromethyl effect on X‐ray absorption that blue shifts the resonant Cu K‐edge energy by 2–3 eV per CF3, completely accounting for observed changes in DAFS profiles between formally Cu(III) complexes like1 and formally Cu(I) complexes like (Ph3P)3CuCF3(3 ). Thus, in agreement with the inverted ligand field model, the data presented herein imply that1 is best described as containing a Cu(I) ion with dncount approaching 10. -
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