Structural and Electronic Characteristics of a Novel BEDT‐TTF Derivative: [BEDT‐TTF]2[Cu2Br3]

Schödel, Frauke; Tutsch, Ulrich; Isselbächer, Friedhelm; Schweitzer, Dieter; Sänger, Inge; Bolte, Michael; Bats, Jan W.; Müller, Jens; Lang, Michael; Lerner, Hans‐Wolfram

doi:10.1002/ejic.201001044

Cited by 5 publications

(1 citation statement)

References 21 publications

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“…The nitrile nitrogen atoms of [N(CN) 2 ] − are considered to carry most of the negative charge in this ion . This is reflected in crystal structures of organic [N(CN) 2 ] − salts, where the nitrile groups are universally involved in a number of interionic short contacts. , In both salts of [(UO 2 (NO 3 ) 2 N(CN) 2 ) 2 ] 2– , interionic contacts are associated only with the central nitrogen atom, not the coordinated atoms. By comparison, coordinating and noncoordinating atoms in the [NO 3 ] − groups are observed to make short contacts to counterions.…”

Section: Results and Discussionmentioning

confidence: 99%

Isolation of Uranyl Dicyanamide Complexes from N-Donor Ionic Liquids

Kelley

Rogers

2015

Inorg. Chem.

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An ionic liquid (IL) approach for soft-donor f-element chemistry has been demonstrated by the isolation of several new uranyl dicyanamide complexes through reactions of UO2(NO3)2·6H2O with dicyanamide ([N(CN)2](-))-containing ILs. The [N(CN)2](-) ions are able to rapidly substitute uranium's O-donor ligands, as evidenced by single-crystal X-ray diffraction studies on two anhydrous adducts of UO2(NO3)2 with [N(CN)2](-) ILs as well as by IR and NMR spectroscopic studies on solutions of UO2(NO3)2 in these ILs. By contrast, the slow reaction of UO2(OAc)2·2H2O with a nitrile-functionalized imidazolium dicyanamide IL in solvent and the reaction of UO2(NO3)2·6H2O with NaN(CN)2 at elevated temperature resulted in irreversible hydrolysis. The reaction of UO2SO4 with [N(CN)2](-) ions in an acidified aqueous solution resulted in the crystallization of a [UO2](2+) complex with biuret, a N(CN)2](-) hydrolysis product. [N(CN)2](-) ions in the form of ILs react rapidly with [UO2](2+) at room temperature, allowing ligand substitution with [N(CN)2](-) to out-compete the slower hydrolysis reaction, enabling the isolation of uranyl dicyanamide complexes and challenging assumptions regarding the affinity of uranium for O-donors.

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Section: Results and Discussionmentioning

confidence: 99%

Isolation of Uranyl Dicyanamide Complexes from N-Donor Ionic Liquids

Kelley

Rogers

2015

Inorg. Chem.

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Design, Synthesis, and Structure of Copper Dithione Complexes: Redox‐Dependent Charge Transfer

et al. 2019

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Redox‐active ligands impart versatility in transition metal complexes, which are attractive for photosensitizers, dye sensitized solar cells, photothermal therapy, etc. Dithiolene (Dt) ligands can transition between fully reduced and fully oxidized states. Herein, we report the syntheses, characterization, crystal structures and electronic properties of four [Cu(R2Dt0)2]+/2+ (R = Me, iPr) complexes, [Cu(iPr2Dt0)2][PF6] (1a), [Cu(iPr2Dt0)2][PF6]2 (1b), and [Cu(Me2Dt0)2][PF6] (2a), [Cu(Me2Dt0)2][PF6]2 (2b), where iPr2Dt0 = N,N′‐diisopropyl‐1,2‐piperazine dithione and Me2Dt0 = N,N′‐dimethyl‐1,2‐piperazine dithione. In addition, the molecular structure of [Cu(iPr2Dt0)2][BF4]2(1c) is also reported. Complexes 1a and 2a crystallized in the triclinic, P1 space group, and 1c crystallized in the monoclinic crystal system, space group C2/c. The single‐crystal X‐ray diffraction measurements show that the Cu(I) complexes have a distorted tetrahedral geometry, whereas the Cu(II) complex exhibits a true square‐planar geometry. Cu(I) complexes exhibit a low energy charge‐transfer band (450–650 nm), which are not observed in Cu(II) complexes. Electrochemical studies of these complexes show both ligand‐ and metal‐based redox couples.

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