Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands
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...
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doaj-e3d3f84aaaee4a39a33654585ee700552020-11-25T00:03:25ZengBeilstein-InstitutBeilstein Journal of Nanotechnology2190-42862017-07-01811375138710.3762/bjnano.8.1392190-4286-8-139Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligandsMartin Börner0Laura Blömer1Marcus Kischel2Peter Richter3Georgeta Salvan4Dietrich R. T. Zahn5Pablo F. Siles6Maria E. N. Fuentes7Carlos C. B. Bufon8Daniel Grimm9Oliver G. Schmidt10Daniel Breite11Bernd Abel12Berthold Kersting13Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, GermanyInstitut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, GermanyInstitut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, GermanySemiconductor Physics, Chemnitz University of Technology, D-09107 Chemnitz, GermanySemiconductor Physics, Chemnitz University of Technology, D-09107 Chemnitz, GermanySemiconductor Physics, Chemnitz University of Technology, D-09107 Chemnitz, GermanyMaterial Systems for Nanoelectronics, Chemnitz University of Technology, Reichenhainer Str. 70, 09107 Chemnitz, GermanyInstitute for Integrative Nanosciences, IFW Dresden, Helmholtz Str. 20, 01069 Dresden, Germany,Institute for Integrative Nanosciences, IFW Dresden, Helmholtz Str. 20, 01069 Dresden, Germany,Institute for Integrative Nanosciences, IFW Dresden, Helmholtz Str. 20, 01069 Dresden, Germany,Institute for Integrative Nanosciences, IFW Dresden, Helmholtz Str. 20, 01069 Dresden, Germany,Leibniz-Institute of Surface Modification (IOM), Permoser Str. 15, D-04318 Leipzig, GermanyLeibniz-Institute of Surface Modification (IOM), Permoser Str. 15, D-04318 Leipzig, GermanyInstitut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, GermanyThe 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.https://doi.org/10.3762/bjnano.8.139ambidentate ligandschemisorptiongold surfacesmacrocyclic complexesmercapto-alkanecarboxylic acid |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Martin Börner Laura Blömer Marcus Kischel Peter Richter Georgeta Salvan Dietrich R. T. Zahn Pablo F. Siles Maria E. N. Fuentes Carlos C. B. Bufon Daniel Grimm Oliver G. Schmidt Daniel Breite Bernd Abel Berthold Kersting |
spellingShingle |
Martin Börner Laura Blömer Marcus Kischel Peter Richter Georgeta Salvan Dietrich R. T. Zahn Pablo F. Siles Maria E. N. Fuentes Carlos C. B. Bufon Daniel Grimm Oliver G. Schmidt Daniel Breite Bernd Abel Berthold Kersting Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands Beilstein Journal of Nanotechnology ambidentate ligands chemisorption gold surfaces macrocyclic complexes mercapto-alkanecarboxylic acid |
author_facet |
Martin Börner Laura Blömer Marcus Kischel Peter Richter Georgeta Salvan Dietrich R. T. Zahn Pablo F. Siles Maria E. N. Fuentes Carlos C. B. Bufon Daniel Grimm Oliver G. Schmidt Daniel Breite Bernd Abel Berthold Kersting |
author_sort |
Martin Börner |
title |
Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
title_short |
Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
title_full |
Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
title_fullStr |
Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
title_full_unstemmed |
Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
title_sort |
deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands |
publisher |
Beilstein-Institut |
series |
Beilstein Journal of Nanotechnology |
issn |
2190-4286 |
publishDate |
2017-07-01 |
description |
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. |
topic |
ambidentate ligands chemisorption gold surfaces macrocyclic complexes mercapto-alkanecarboxylic acid |
url |
https://doi.org/10.3762/bjnano.8.139 |
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