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Conductive Self-Assembled Monolayers of Paramagnetic {Co^II Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.

ABSTRACT: Two polynuclear cobalt(II,III) complexes, [Co₅(N₃)₄(N-n-bda)₄(bza·SMe)₂] (1) and [Co₆(N₃)₄(N-n-bda)₂(bza·SMe)₅(MeOH)₄]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H₂bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhibits an unusual, approximately C ₂-symmetric {Co^II Co 4 III } core of two isosceles Co₃ triangles with perpendicularly oriented planes, sharing a central, high-spin Co^II ion residing in a distorted tetrahedral coordination environment. This central Co^II ion is connected to four outer, octahedrally coordinated low-spin Co^III ions via oxo bridges. Compound 2 comprises a semi-circular { Co 4 II Co 2 III } motif of four non-interacting high-spin Co^II and two low-spin Co^III centers in octahedral coordination environments. Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed on template-stripped gold surfaces contacted by an eutectic gallium-indium (EGaIn) tip. The acquired current density-voltage (I-V) data revealed that the cobalt-based SAMs are more electrically robust than those of the previously reported dinuclear {Cu^IILn^III} complexes with Ln = Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition, between 170 and 220°C, the neutral, mixed-valence compound 1 undergoes a redox modification, yielding a {Co₅}-based coordination cluster (1-A) with five non-interacting, high-spin octahedral Co^II centers as indicated by SQUID magnetometry analysis in combination with X-ray photoelectron spectroscopy and infrared spectroscopy. Solvothermal treatment of 1 results in a high-nuclearity coordination cluster, [Co₁₀(N₃)₂(N-n-bda)₆(bza·SMe)₆] (3), containing 10 virtually non-interacting high-spin Co^II centers.

SUBMITTER: Schmitz S

PROVIDER: S-EPMC6848059 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

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Conductive Self-Assembled Monolayers of Paramagnetic {CoII Co4III } and { Co4II Co2III } Coordination Clusters on Gold Surfaces.

Schmitz Sebastian S Qiu Xinkai X Glöß Maria M van Leusen Jan J Izarova Natalya V NV Nadeem Muhammad Arif MA Griebel Jan J Chiechi Ryan C RC Kögerler Paul P Monakhov Kirill Yu KY

Frontiers in chemistry 20191105

Two polynuclear cobalt(II,III) complexes, [Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and [Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhib ...[more]

PMID: 31750287

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Project description:Gold nanoparticles (AuNPs) with 14, 25 and 40nm diameters were functionalized with different chain length (C6, C8, C11 and C16) carboxylic acid terminated alkanethiol self-assembled monolayers (COOH-SAMs). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to examine the changes in surface chemistry as both AuNP diameter and SAM chain length were varied. COOH-SAMs on flat gold surfaces were also examined and compared to the COOH-SAM on AuNP results. For a given surface, as the COOH-SAM chain length increased the XPS C/Au atomic ratio increased due to an increased number of carbon atoms per molecule in the overlayer and an increased attenuation of the Au substrate signal. For the C16 COOH-SAMs, as the size of AuNPs decreased the XPS C/Au atomic ratio and the apparent SAM thickness increased due to the increased curvature of the smaller AuNPs. The C16 COOH-SAMs on the flat Au had the lowest XPS C/Au atomic ratio and apparent SAM thickness of any C16 COOH-SAM covered Au surface. The effective take-off angles of the COOH-SAMs were also calculated by comparing the apparent thickness of COOH-SAMs with literature values. The effective take-off angle for C16 COOH-SAM on 14nm, 25nm and 40nm diameter AuNPs and flat Au were found to be 57°, 53°, 51° and 39°, respectively, for data acquired in a mode that collects a wide range of photoelectron take-off angles. The effective take-off angle for C16 COOH-SAM on 14nm AuNP and flat Au decreased to 52° and 0°, respectively, for data acquired in a mode that collects a narrow range of photoelectron take-off angles. The ToF-SIMS results showed similar changes in surface chemistry with COOH-SAM chain length and AuNP size. For example, the ratio of the sum of the C(1-4)H(x)O(y) positive ion intensities to the sum of the Au-containing positive ions intensities increased with decreasing AuNP size and increasing COOH-SAM chain length. Fourier transform IR spectroscopy in the attenuated total reflectance mode (FTIR-ATR) was used to characterize the crystallinity of the COOH-SAMs. The CH(2) stretching frequencies decreased with increasing COOH-SAM chain length on flat Au. The C16 COOH-SAM on the 14nm AuNPs exhibited a crystalline-like CH(2) stretching frequency. The size, size distribution, shapes and solution stability of AuNPs were investigated with transmission electron microscopy (TEM) and UV/VIS spectroscopy. As the average diameter of the AuNPs decreased the size distribution became narrower and the shape became more spherical.

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Conductive Self-Assembled Monolayers of Paramagnetic {Co^II Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.

Publications

Conductive Self-Assembled Monolayers of Paramagnetic {Co<sup>II</sup> Co4III } and { Co4II Co2III } Coordination Clusters on Gold Surfaces.

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Dataset Information

Conductive Self-Assembled Monolayers of Paramagnetic {CoII Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.

Publications

Conductive Self-Assembled Monolayers of Paramagnetic {Co<sup>II</sup> Co4III } and { Co4II Co2III } Coordination Clusters on Gold Surfaces.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Conductive Self-Assembled Monolayers of Paramagnetic {Co^II Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.