A pentaammineruthenium mixed-valence complex with 1,4-dicyanamido-2,3,5,6-tetrachlorobenzene dianion as bridging ligand: symmetry-attenuated electronic coupling between redox sites

Aquino, Manuel A.S.; Bostock, Ann E.; Crutchley, Robert J.

doi:10.1021/ic00344a005

Cited by 17 publications

(6 citation statements)

References 2 publications

(3 reference statements)

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“…The preparations of the tetraphenylarsonium salts of 1,4-dicyanamidebenzene dianion (Dicyd 2-), 1,4-dicyanamide-2,5-dimethylbenzene dianion (Me2Dicyd 2-) and 2,5-dichloro-l,4-dicyanamidebenzene dianion (C12Dicyd 2-) follow essentially the same procedure as that for 2,3,5,6-tetrachloro-l,4-dicyanamidebenzene dianion (C14Dicyd 2-) which has been published (Aquino, Bostock & Crutchley, 1990). Unlike the tetrachloro derivative, these compounds can be easily isolated pure in their neutral protonated form.…”

Section: N~c (I) (Ii)mentioning

confidence: 99%

Structure of 1,4-benzenedicyanamide dianion derivatives

Aquino¹,

Crutchley²,

Lee³

et al. 1993

Acta Crystallogr C

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Section: N~c (I) (Ii)mentioning

confidence: 99%

Structure of 1,4-benzenedicyanamide dianion derivatives

Aquino¹,

Crutchley²,

Lee³

et al. 1993

Acta Crystallogr C

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“…Abstract: A family of magnetic metal-organic frameworks, (Ph 3 PMe) 2 [M 2 (TCNQ) 3 ] {M= Fe 2 + , Co 2 + , Ni 2 + and Zn 2 + } have been prepared and structurally characterized. The honeycomb-like "layers" consist of M II ions doubly bridged with dinitrilomethane moieties of two 7,7, 8, dianions which are further connected through phenyl rings to form a 3D dianionic framework [M 2 TCNQ 3 ] 2À with Ph 3 PMe + cations filling cavities that run along the c axis.…”

mentioning

confidence: 99%

“…[6c] Also, Kitagawa and co-workers reported similar coordination polymers containing the TCNQ 2À dianion that were found to exhibit unusual charge-transfer interactions with guest molecules. [7] As an extension of this work in the context of magnetism, herein we report the synthesis and magnetic studies of a family of 3D coordination polymers based on the TCNQ dianion of general formula ( 3 ] products were harvested after slow diffusion for several days. X-ray structures revealed that all of the compounds are isostructural and crystallize in the trigonal space group R-3c as three dimensional [M II 2 -(TCNQ IIÀ ) 3 ] 2À anionic networks, in which one type of m 4 -TCNQ 2À unit is coordinated to independent M II ions.…”

mentioning

confidence: 99%

“…Among the intriguing results in this area are findings involving fully reduced organocyanide ligands that are well suited for intramolecular electronic and magnetic communication. In this vein, the bridging ligand, 1,4-dicyanamidebenzene dianion ([1,4dicyd] 2À ), has been shown by Crutchley and co-workers to be an extremely efficient mediator of electronic and magnetic coupling between Ru II and Ru III ions in spite of a separation between the metal centers of over 13 , [3] results that are attributed to an energetically favorable match between the p HOMO of [1,4-dicyd] 2À and the dp orbitals of the ruthenium ions. Using the structural parameters from X-ray studies of Crutchley's compounds, Ruiz and co-workers performed DFT calculations on hypothetical dinuclear trivalent 3D transitionmetal model compounds.…”

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confidence: 99%

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Magnetic Coupling between Metal Spins through the 7,7,8,8‐Tetracyanoquinodimethane (TCNQ) Dianion

Saber

Prosvirin

Abrahams

et al. 2014

Chemistry A European J

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A family of magnetic metal-organic frameworks, (Ph3PMe)2[M2(TCNQ)3] {M=Fe(2+), Co(2+), Ni(2+) and Zn(2+)} have been prepared and structurally characterized. The honeycomb-like "layers" consist of M(II) ions doubly bridged with dinitrilomethane moieties of two 7,7,8,8-tetracyanoquinodimethane (TCNQ) dianions which are further connected through phenyl rings to form a 3D dianionic framework [M2TCNQ3](2-) with Ph3PMe(+) cations filling cavities that run along the c axis. Studies of the magnetic coupling through the TCNQ dianion in these structures revealed that it can promote long-range magnetic ordering despite the long coupling pathway.

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“…C, H, and N elemental analyses were performed by Canadian Microanalytical Services Ltd. The experimental setup used to perform non-aqueous (13) and aqueous (14) cyclic voltammetry experiments has alread been described. The ferricenium/ferrocene couple with E6= 665 mV vs. NHE (15) was used in nonaqueous solvents as an internal calibrant.…”

Section: Physical Measurementsmentioning

confidence: 99%

A pentaammineruthenium(III) dimer with the novel bridging ligand 4,4′-dicyanamidobiphenyl dianion

Aquino¹,

White²,

Bensimon³

et al. 1996

Can. J. Chem.

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The novel ligand 4,4′-dicyanamidobiphenyl dianion (bp2−) has been synthesized and characterized by 13C NMR spectroscopy, cyclic voltammetry, and crystallography. The crystal structure of [Ph4As]2[bp]•H2O showed that bp2− is approximately planar with a dihedral angle of 8.2° between phenyl ring planes and the cyanamide groups in an anti conformation. The water of crystallization is asymmetrically hydrogen bonded between cyanamide groups of adjacent bp2− ions. The crystal data for C62H48N4As2 + H2O are monoclinic crystal system and space group P21/c with a = 12.998(5) Å, b = 13.465(4) Å, c = 28.703(13) Å, β = 98.94(3)°, V = 4963(3) Å3 and Z = 4. The structure was refined by using 4555 reflections with I > 2.5σ(I) to an R factor of 0.058. The complex, [{(NH3)5Ru)2(μ-bp)][X]4, where X = tosylate or PF6− ions, was also synthesized and characterized by 1H NMR spectroscopy, cyclic voltammetry, spectroelectrochemistry, and temperature-dependent magnetic susceptibility measurements. From cyclic voltammetry measurements, the comproportionation constants to form the mixed-valence complex [{(NH3)5Ru)2(μ-bp)]3+ were estimated to be 4.1, 16, and 22 in water, acetonitrile, and nitromethane, respectively. The trend and magnitude of Kc suggests solvent valence trapping of a weakly coupled Class II ion. The MMCT band of the mixed-valence complex had to be deconvoluted from the low-energy LMCT band and had the following properties in acetonitrile, νmax = 8400 cm−1, εmax = 3300 M−1 cm−1, and Δν1/2 = 3300 cm−1. The weak superexchange mediating properties of bp2− compared to 1,4-dicyanamidobenzene dianion were suggested to arise from the larger barrier to the formation of the radical anion bp−. Key words: cyanamido, mixed valence, superexchange, ruthenium.

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A pentaammineruthenium mixed-valence complex with 1,4-dicyanamido-2,3,5,6-tetrachlorobenzene dianion as bridging ligand: symmetry-attenuated electronic coupling between redox sites

Cited by 17 publications

References 2 publications

Structure of 1,4-benzenedicyanamide dianion derivatives

Structure of 1,4-benzenedicyanamide dianion derivatives

Magnetic Coupling between Metal Spins through the 7,7,8,8‐Tetracyanoquinodimethane (TCNQ) Dianion

A pentaammineruthenium(III) dimer with the novel bridging ligand 4,4′-dicyanamidobiphenyl dianion

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