Ferrimagnetic ordering of one-dimensional N,N′-dicyanoquinone diimine (DCNQI) electron transfer salts with porphyrinatomanganese(II)

Sugiura, Ken Ichi; Mikami, Shinji; Johnson, Mark D.; Raebiger, James W.; Miller, Joel S.; Iwasaki, Kentaro; Okada, Y.; Hino, Shinjiro; Sakata, Yoshiteru

doi:10.1039/b100936m

Cited by 23 publications

(24 citation statements)

References 45 publications

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“…2+ . This structure is intermediate between the benzenic structure of the dianion dicyd 2and the quinonic structure of DCNQI (dicyd 0 ) as shown for dicyd .salts with porphyrinatomanganese(II) 31. …”

mentioning

confidence: 81%

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

et al. 2006

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The dicyanamidobenzene-bridge diruthenium complex [{Ru(tpy)(thd)}(2)(mu-dicyd)][PF(6)] ([3][PF(6)]) (dicyd = 1,4-dicyanamidobenzene, tpy = 2,2':6',2' '-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and its mononuclear counterpart [Ru(tpy)(thd)(Ipcyd)] (2) [Ipcyd = 4-iodophenylcyanamide anion (Ipcyd(-))] were synthesized and fully characterized. Cyclic voltammetry of 3 showed the presence of four reversible one-electron redox couples. UV-vis-NIR spectroelectrochemistry and EPR spectroscopy of the electrogenerated paramagnetic intermediates were used to ascertain the oxidation-state distribution. The stable starting dinuclear complex 3(+) is found to be a ligand-centered anion radical as shown by EPR spectroscopy, magnetic susceptibility measurements, and DFT calculations. Oxidation of 3(+) to 3(2+) led to an EPR silent system due to substantial intramolecular antiferromagnetic interaction of the electron spins carried by the low spin ruthenium(III) atom and the bridging anion radical dicyanamido (dicyd(*)(-)), an observation which was supported by UV-vis-NIR, X-ray structure, and DFT calculations. Complex 3(3+) presented an EPR spectra consistent with a total effective spin S = (1)/(2) issued from an antiferromagnetic interaction of electron spins carried by two low spin ruthenium(III) atoms and the bridging anion radical dicyd(*)(-) in accordance with UV-vis-NIR. This study shows that the dicyanamidobenzene bridging ligand has indubitably a noninnocent behavior.

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mentioning

confidence: 81%

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

et al. 2006

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“…The oxidation state of DMDCNQI (A dÀ ), which acts as the acceptor, must correspond to the oxidation state of the [Ru 2 ] unit, which acts as the donor, and these can be determined by comparing the DMDCNQI bond lengths in the Kistenmacher relationship, [27] II,II (CF 3 CO 2 ) 4 -(DMDCNQI)] is the neutral form (d = 0), [28] and that [Mn III -(TMesP)(DMDCNQI)] (TMesP = meso-tetrakis(2,4,6-trimethylphe- nyl)porphyrinate) is the ionic form (d = 1), [29] in which the b, c, and d bonds are defined in the DMDCNQI chart shown in Scheme 1. Neutral DMDCNQI has a quinonoid structure in which each bond has a characteristic bonding multiplicity, these being single (CÀN or CÀC; b and d), double (C=C; c and e), or triple (C N; a) bonds, whereas anionic DMDCNQI (i.e., DMDCNQIC À ) has an almost benzenoid structure, with an unpaired electron delocalized over the entire complex, which causes the bond lengths to be averaged ( Figure S5 in the Supporting Information).…”

Section: N-i Transitions From a Structural Viewpointmentioning

confidence: 99%

Systematic Tuning and Switching of Neutral and Ionic Phases in a Donor–Acceptor Chain Compound by Doping with Less‐Active Donors and by Pressure Application

Nakabayashi

Miyasaka

2014

Chemistry A European J

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The temperature-induced stepwise neutral-ionic (N-I) phase transition in the covalently bonded donor-acceptor chain compound [Ru2 (2,3,5,6-F4 PhCO2 )4 DMDCNQI]⋅ 2(p-xylene) (2,3,5,6-F4 PhCO2 (-) =2,3,5,6-tetrafluorobenzoate; DMDCNQI=2,5-dimethyl-N,N'-dicyanoquinodiimine) was systematically tuned over a wide temperature range using two techniques: 1) A chemical technique based on doping with a less-active donor unit [Ru2 (II,II) (F5 PhCO2 )4 ] (F5 PhCO2 (-) =pentafluorobenzoate), thereby providing an isostructural doped series [{Ru2 (II,II) (2,3,5,6-F4 PhCO2 )4 }1-x {Ru2 (II,II) (F5 PhCO2 )4 }x DMDCNQI]⋅2(p-xylene), with x=0.06, 0.10, 0.21, and 0.24; and 2) a physical technique, which was the application of hydrostatic pressure to the doped compounds. The stepwise N-I transition observed in the original compound was systematically varied in terms of the viewpoints of both transition temperature and transition features (stepwise or monotonic) dependent on the amount of dopants x. Application of pressure efficiently tuned the N-I transitions, with the oxidation phases being dramatically modified by applying only weak pressure up to 4 kbar. Even in cases that led to N-I transitions in small domains of the chains at ambient pressure, the application of pressure caused an expansion of the domains that enabled N-I transitions, finally leading to a complete change in the oxidation state of the chains, from neutral to ionic, accompanied by a change from a paramagnetic state to a ferrimagnetically ordered state.

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“…For complex II , Mn(2p3/2) and Mn(2p1/2) are relatively insensitive to the valency states of Mn . Two peaks for Mn(2p3/2) indicated obviously two valences of metal ion . The XPS results can provide additional evidence supporting the valence of the cobalt ions and manganese ions as measured by ESI‐MS.…”

Section: Resultsmentioning

confidence: 82%

Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure, DNA binding and DNA cleavage

Yin

Wen

Geng

et al. 2012

Applied Organom Chemis

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4,7,10-tetra-(2-hydroxypropyl)-l,4,7,10-tetraazacyclododecane] using electrospray ionization mass spectrometry and X-ray photoelectron spectrometery. The characterizations confirmed that the valences of the metal ions increased from divalent to trivalent due to deprotonation of one OH group (H 4 L was in the form of H 3 L À ). Owing to the instability of Co(III) and Mn(III) in both air and in solution, they preferred to exist in divalent form. The two heptadentate complexes are extraordinary in that the chiral pendants of the complexes are different in configuration. Spectroscopic studies, viscosity measurements, thermal denaturation experiments and circular dichroism spectra demonstrated that the complexes were prone to interact with DNA by groove binding. At micromolar concentrations and under physiological conditions, the two complexes were able to oxidatively cleave the supercoiled pUC19 plasmid DNA into its nicked and linear forms. Mechanistic studies using various additives suggest the complexes had structures different from those of other inorganic complexes. These are the first reported inorganic complexes not containing planar aromatic ligands and yet binding at the major groove.

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Ferrimagnetic ordering of one-dimensional N,N′-dicyanoquinone diimine (DCNQI) electron transfer salts with porphyrinatomanganese(II)

Cited by 23 publications

References 45 publications

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

Systematic Tuning and Switching of Neutral and Ionic Phases in a Donor–Acceptor Chain Compound by Doping with Less‐Active Donors and by Pressure Application

Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure, DNA binding and DNA cleavage

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Ferrimagnetic ordering of one-dimensional N,N′-dicyanoquinone diimine (DCNQI) electron transfer salts with porphyrinatomanganese(II)

Cited by 23 publications

References 45 publications

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}2(μ-dicyd)][PF6] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}2(μ-dicyd)][PF6] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

Systematic Tuning and Switching of Neutral and Ionic Phases in a Donor–Acceptor Chain Compound by Doping with Less‐Active Donors and by Pressure Application

Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure, DNA binding and DNA cleavage

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On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}₂(μ-dicyd)][PF₆] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione