Hetero Cu(III)--Pd(II) Complex of a Dibenzo[g,p]chrysene-Fused Bisdicarbacorrole with Stable Organic Radical Character.
Bis-dicarbacorrole (bis-H) with two adj-CCNN subunits was synthesized by incorporating a dibenzo[g,p]chrysene moiety into the macrocyclic structure. The two trianionic cores in bis-H can stabilize two Cu(III) ions (bis-Cu) or concurrently a Cu(III) cation and a Pd(II) ion in the form of a hetero bis...
| Published in: | Journal of the American Chemical Society Vol. 139; no. 42; pp. 15232 - 15239 |
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| Main Authors: | , , , , , , |
| Format: | Article |
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American Chemical Society
10/25/2017
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=125899038&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 125899038 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/25/2017 vid: 139 iid: 42 pid: 997 pub: American Chemical Society artinfo: ui: 125899038 10.1021/jacs.7b09167 ppf: 15232 ppct: 7 formats: tig: atl: Hetero Cu(III)--Pd(II) Complex of a Dibenzo[g,p]chrysene-Fused Bisdicarbacorrole with Stable Organic Radical Character. aug: au: Xian-Sheng Ke Yongseok Hong Peiyu Tu Qing He Lynch, Vincent M. Dongho Kim Sessler, Jonathan L. affil: Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United States Department of Chemistry, Yonsei University, Seoul 03722, Korea su: Chrysene Electron paramagnetic resonance spectroscopy Cyclic voltammetry Density functional theory Current density (Electromagnetism) sug: subj: Chrysene Electron paramagnetic resonance spectroscopy Cyclic voltammetry Density functional theory Current density (Electromagnetism) ab: Bis-dicarbacorrole (bis-H) with two adj-CCNN subunits was synthesized by incorporating a dibenzo[g,p]chrysene moiety into the macrocyclic structure. The two trianionic cores in bis-H can stabilize two Cu(III) ions (bis-Cu) or concurrently a Cu(III) cation and a Pd(II) ion in the form of a hetero bis-metal complex (mix-Cu/Pd). As prepared, mix-Cu/Pd displays organic π radical character, as confirmed by various techniques, including electron paramagnetic resonance spectroscopy, cyclic voltammetry, femtosecond transient absorption measurements and DFT calculations. Radical formation is ascribed to one-electron transfer from the dicarbacorrole backbone to the Pd center allowing the d Pd(II) center to be accommodated in a square planner coordination geometry. Nucleus-independent chemical shift and anisotropy of the induced current density calculations provide support for the conclusion that bis-H and bis-Cu both display antiaromatic character and contain two formally 16 π-electron dicarbacorrole subunits. On this basis, we suggest that mix-Cu/Pd is best considered as containing a fused 15 π-electron nonaromatic radical subunit and a 16 π-electron antiaromatic subunit. The spectroscopic observations are consistent with these assignments. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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