Lindsay M. Hinkle

University of Minnesota Duluth, Duluth, Minnesota, United States

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Publications (6)13.75 Total impact

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    ABSTRACT: We report the synthesis and characterization for several gold(III) complexes involving a series of cyclometallating ligands. These cyclometallating ligands (CˆN) are: 2-phenylpyridine (ppy), 2-(p-tolyl)pyridine (tpy), 2-(2′-benzothienyl)pyridine (btp) and 7,8-benzoquinoline (bzq). With the assistance of TGA data, we have developed solventless reactions to prepare the neutral cyclometallated Au(III) dichloro complexes. Reaction of these with the crown trithioether [9]aneS3 (1,4,7-trithiacyclononane), followed by metathesis with NH4PF6, yields the heteroleptic complexes [Au([9]aneS3)(CˆN)](PF6)2. The X-ray structures of the gold(III) [9]aneS3 complexes display axial Au–S interactions formed by the endodentate conformation of the thiacrown, resulting in elongated square pyramidal geometries. The Au–S axial distance correlates with the electron-donating properties of the CˆN ligand with the better donating btp showing the longest distance (2.855(1) Å) while the ppy shows the shortest (2.818(1) Å). The coordinated [9]aneS3 ligand shows fluxional behavior by its NMR spectroscopy, resulting in a single 13C NMR resonance despite the asymmetric coordination environment of the cyclometallating ligand. Electrochemical studies of the [9]aneS3 complexes reveal irreversible one-electron reductions which are assigned as a Au(III)/Au(II) couple. The ease of reduction correlates with the axial Au–S distances with the btp being the easiest to reduce and the ppy the most difficult. In addition, we report the crystal structures for three intermediate complexes: [Au(H-tpy)Cl3], [Au(H-btp)Cl3], and [Au(btp)Cl2]. The [Au(H-btp)Cl3] complex shows an interesting Au–S axial interaction at 3.139(2) Å which alters the physicochemical properties of the complex.
    Journal of Organometallic Chemistry 04/2014; 755:47–57. DOI:10.1016/j.jorganchem.2013.12.048 · 2.17 Impact Factor
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    ABSTRACT: The crystal structures of a related series of isosteric compounds, namely tritylnitrile 1, tritylisonitrile 2, and a solid solution of tritylnitrile/tritylisonitrile 3 have been determined by single crystal X-ray diffraction. The bond lengths, angles, and intermolecular interactions do not deviate significantly from previously reported nitriles and isonitriles. These isosteric compounds pack in nonisomorphous but very similar structures. Subtle differences between the packing of 1 and 2 are detailed. The solid solution of tritylnitrile/tritylisonitrile 3 is isomorphous with the structure of tritylnitrile 1. This solid solution possesses substitutional disorder involving the nitrile and isonitrile groups (Z′ = 2, nitrile/isonitrile occupancy ratios 53.7/46.3 and 54.6/45.4). The structure of tritylisonitrile 2 possesses positional disorder over two sites (Z′ = 2, occupancy ratio of 93.1/6.9). A comparison with previously reported nearly isosteric structures reveals that other chemically dissimilar compounds crystallize in each of the two molecular packing arrangements described in this report. Structure 1: monoclinic, P21/c, a = 18.049(11) Å, b = 9.583(6) Å, c = 17.824(11) Å, β = 108.680(10)°, V = 2921(3) Å3, Z = 8, R 1 = 0.0467, wR 2 = 0.1491. Structure 2: triclinic, P 1− , a = 9.5877(13) Å, b = 10.7479(14) Å, c = 14.809(2) Å, α = 88.457(2)°, β = 80.303(2)°, γ = 77.128(2)°, V = 1466.4(3) Å3, Z = 4, R 1 = 0.0423, wR 2 = 0.1151. Structure 3: monoclinic, P21/c, a = 18.03464(15) Å, b = 9.5739(8) Å, c = 17.8251(11) Å, β = 108.5920(10)°, V = 2917.4(4) Å3, Z = 8, R 1 = 0.0587, wR 2 = 0.1734.
    Journal of Chemical Crystallography 09/2012; 42(9):972-980. DOI:10.1007/s10870-012-0345-2 · 0.50 Impact Factor
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    Lindsay M Hinkle · Raghu Chitta · Kent R Mann ·
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    ABSTRACT: The title compound, C8H12N+·C20H18BF2N2O2 −, crystallizes with a significant amount of void space [4.0 (5)%] in the unit cell. The structure displays N—H⋯O hydrogen bonding between the components. The plane formed by the benzoic acid moiety of the BODIPY-CO2 − is twisted by 80.71 (6)° relative to the plane formed by the ring C and N atoms of the tetramethyldipyrrin portion of the molecule.
    Acta Crystallographica Section E Structure Reports Online 09/2011; 67(Pt 9):o2265-6. DOI:10.1107/S1600536811019167 · 0.35 Impact Factor
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    ABSTRACT: Oligothiophene-substituted 1,1,4,4-tetracyanobutadienes (TCBDs) have been synthesized by [2 + 2] cycloaddition reactions between tetracyanoethylene and oligothiophene alkynes. The TCBD moiety is compared to other electron acceptors attached to dibutylterthiophene including dicyanovinyl (DCV) and tricyanovinyl (TCV). These donor−acceptor molecules (TCBD-3T, DCV-3T, and TCV-3T) show red-shifted absorption spectra relative to the unsubstituted oligothiophene as a result of intramolecular charge-transfer (ICT). Monosubstituted terthiophenes bearing the electron acceptors show both oxidation and reduction processes as characterized by cyclic voltammetry. Density functional theory (DFT) calculations are used to explain the electronic and redox properties of the materials. Electrochemical oxidation of a bis(terthienyl)-substituted TCBD molecule (3T-TCBD-3T) yields a conducting polymer exhibiting balanced ambipolar redox conduction with similar values for the oxidized and reduced states of the polymer (1 × 10−3 S cm−1). Raman spectra of the asymmetric donor−acceptor materials are characterized by two intense bands characteristic of the aromatic and quinoidal regions in the conjugated π-system of the oligothiophene.
    Chemistry of Materials 02/2011; 23:823-831. DOI:10.1021/cm102128g · 8.35 Impact Factor
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    ABSTRACT: New direct syntheses of [Pt(trpy)(NCCH3)](CF3SO3)22 (where trpy = 2,2′:6′,2′′-terpyridine) and [Pt(tBu3-trpy)(NCCH3)](CF3SO3)23 (where tBu3-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH3)4](CF3SO3)2 have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh3), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5-diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh3, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF3SO3) 6. The structures of [Pt(trpy)L]2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu3-trpy complex 3 which exists as head-to-tail dimers with a Pt–Pt distance of 3.29 Å. The cyano product 6 was found to stack in infinite chains of cations with a Pt–Pt distance of 3.45 Å.
    Inorganica Chimica Acta 10/2010; 363(13):3214–3221. DOI:10.1016/j.ica.2010.05.060 · 2.05 Impact Factor
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    Lindsay M Hinkle · Victor G Young · Kent R Mann ·
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    ABSTRACT: The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl(3)(C(22)H(17)N(3))] x C(2)H(6)OS, (I), is presented, along with a higher-symmetry setting of previously reported bis[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C(22)H(17)N(3))(2)](PF(6))(3) x 2 C(2)H(3)N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF(6)(-) anion lie on twofold axes in this structure, making half of the molecule unique.
    Acta Crystallographica Section C Crystal Structure Communications 03/2010; 66(Pt 3):m62-4. DOI:10.1107/S0108270110002751 · 0.33 Impact Factor