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. 2010 Oct 15;363(12):2857-2864.
doi: 10.1016/j.ica.2010.04.004.

Synthesis, characterization, spectroscopy, electronic and redox properties of a new nickel dithiolene system

Partha Basu  1 , Archana Nigam, Benjamin Mogesa, Suzanne Denti, Victor Nemykin
Affiliations

Synthesis, characterization, spectroscopy, electronic and redox properties of a new nickel dithiolene system

Partha Basu et al. Inorganica Chim Acta. .

Abstract

A new dithiolene ligand with 3,5-dibromo substituted phenyl groups was designed and synthesized. The protected form of the ligand was reacted with a nickel salt providing neutral Ni(S(2)C(2)(3,5-C(6)H(3)Br(2))(2))(2) and anionic [Ni(S(2)C(2)(3,5-C(6)H(3)Br(2))(2))(2)](-) isolated as a Bu(4)N(+) salt. Both were characterized by UV-visible and IR spectroscopy and compared with the similar known molecular systems. They exhibit intense low-energy transitions that are characteristic of such systems. The electrochemical behavior of these molecules was investigated by cyclic voltammetry.

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Figures

Figure 1
Figure 1
The compounds used in this investigation.
Figure 2
Figure 2
Electronic spectra of Ni-complexes recorded at room temperature. 1a, 1b, 2a, and 2b were recorded in CH2Cl2. 3b and 3c were recorded in CH3CN.
Figure 3
Figure 3
Room temperature cyclic voltammogram of 1a in CH2Cl2.
Figure 4
Figure 4
Thermal ellipsoid (50% probability) representation of molecular structure of [NEt4] [Ni(S2C2(CN)2)2].
Figure 5
Figure 5
Packing diagram of [NEt4][Ni(S2C2(CN)2)2].
Figure 6
Figure 6
Molecular orbital diagram of 3b, 2b, and 1b calculated in spin unrestricted DFT method. The dashed line represents the separation between the HOMO and the LUMO. The formal oxidation state of Ni in these complexes is considered to be +3.
Figure 7
Figure 7
Molecular orbital diagram of 3c (a), 2a (b) and 1a (c) calculated in spin restricted DFT method. The dashed line represents the separation between the HOMO and the LUMO.
Figure 8
Figure 8
Pictorial representation of the HOMOs. The complexes are arranged vertically in order of increasing charge. The left panel shows complex 3 while the right panel shows complex 2.
Scheme I
Scheme I
See this image and copyright information in PMC

References

    1. Tanaka H, Okano Y, Kobayashi H, Suzuki W, Kobayashi A. Science. 2001;291:285. - PubMed
    1. Oliver SN, Kershaw SV, Underhill AE, Hill CAS, Charlton A. MCLC S&T, Section B: Nonlinear Optics. 1995;10:87.
    1. Wang K, Stiefel EI. Science. 2001;291:106. - PubMed
    1. Mueller-Westerhoff UT, Vance B, Yoon DI. Tetrahedron. 1991;47:909.
    1. Baudron SA, Avarvari N, Batail P. Inorg Chem. 2005;44:3380. - PubMed
    2. Cho JY, Domercq B, Jones SC, Yu J, Zhang X, An Z, Bishop M, Barlow S, Marder SR, Kippelen B. J Mater Chem. 2007;17:2642.
    3. Cho JY, Fu J, Padilha LA, Barlow S, Van Stryland EW, Hagan DJ, Bishop M, Marder SR. Mol Cryst Liq Cryst. 2008;485:915.
    4. Hill CAS, Charlton A, Underhill AE, Malik KMA, Hursthouse MB, Karaulov AI, Oliver SN, Kershaw SV. J Chem Soc, Dalton Trans: Inorg Chem. 1995:587.
    5. Jeannin O, Clerac R, Fourmigue M. Chem Mater. 2007;19:5946.

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