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Author: Grimm, Daniel × Author: Schmidt, Oliver G. × Author: Siles, Pablo F. × End date: 2019 × Start date: 2011 ×

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    Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands
    (Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2017) Börner, Martin; Blömer, Laura; Kischel, Marcus; Richter, Peter; Salvan, Georgeta; Zahn, Dietrich R. T.; Siles, Pablo F.; Fuentes, Maria E. N.; Bufon, Carlos C. B.; Grimm, Daniel; Schmidt, Oliver G.; Breite, Daniel; Abel, Bernd; Kersting, Berthold
    The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.
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    Optical properties and electrical transport of thin films of terbium(III) bis(phthalocyanine) on cobalt
    (Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2014) Robaschik, Peter; Siles, Pablo F.; Bülz, Daniel; Richter, Peter; Monecke, Manuel; Fronk, Michael; Klyatskaya, Svetlana; Grimm, Daniel; Schmidt, Oliver G.; Ruben, Mario; Zahn, Dietrich R.T.; Salvan, Georgeta
    The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFMbased electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution.