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. 2016 Mar 4;9(3):167.
doi: 10.3390/ma9030167.

Nanostructured Thin Films Obtained From Fischer Aminocarbene Complexes

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Free PMC article

Nanostructured Thin Films Obtained From Fischer Aminocarbene Complexes

Rosa E Lazo-Jiménez et al. Materials (Basel). .
Free PMC article

Abstract

The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO)₅NH(CH₂)15CH₃, where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir-Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

Keywords: LB films; carbene complexes; ferrocene derivatives; nanostructures; thin films.

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis of Fischer aminocarbenes of ferrocenyl 2(a-b) and phenyl 4(a-b) complexes.
Figure 1
Figure 1
UV–VIS spectra of: (a) 2b and (b) 4b aminocarbene complexes in CHCl3 solution.
Figure 2
Figure 2
Surface pressure vs. area isotherm of ferrocenyl aminocarbene complex 2a, M = Cr.
Figure 3
Figure 3
BAM images (width: 500 µm) of the 2a compound at different surface pressures: (a) 0.5 mN·m−1, (b) 3.0 mN·m−1, (c) 7.0 mN·m−1, and (d) 35.0 mN·m−1.
Figure 4
Figure 4
Surface pressure vs. area isotherm of phenyl aminocarbene complex 4a, M = Cr.
Figure 5
Figure 5
BAM images (width: 500 µm) of the 4a compound at different surface pressures: (a) 0.5 mN·m−1, (b) 3.0 mN·m−1, (c) 7.0 mN·m−1, and (d) 14.0 mN·m−1.
Figure 6
Figure 6
Surface pressure vs. molecular area isotherm of ferrocenyl aminocarbene complex 2b, M = W. Inset shows reversibility of two successive compression-expansion cycles.
Figure 7
Figure 7
BAM images (width: 500 µm) of the 2b compound at different surface pressures: (a) 0.5 mN·m−1, (b) 5.0 mN·m−1, (c) 10.0 mN·m−1, and (d) 25.0 mN·m−1.
Figure 8
Figure 8
Surface pressure vs. molecular area isotherm of phenyl aminocarbene complex 4b, M = W. Inset shows the reversibility of two successive compression-expansion cycles.
Figure 9
Figure 9
BAM images (width: 500 µm) of the 4b compound at different surface pressures: (a) 0.5 mN·m−1, (b) 3.0 mN·m−1, (c) 12.0 mN·m−1, and (d) 35.0 mN·m−1.
Figure 10
Figure 10
UV–VIS absorption spectra of LB films with 10 layers: (a) 2b and (b) 4b. Inset: Absorbance versus the number of layers at: (a) 252 nm and (b) 290 nm.
Figure 11
Figure 11
AFM micrograph of 2b monolayer film: frontal and 3D views, respectively.
Figure 12
Figure 12
AFM micrographs of 4b monolayer film: frontal and 3D views, respectively.
Figure 13
Figure 13
AFM micrographs of 4b double-layer film: Frontal and 3D views, respectively.
Figure 14
Figure 14
3D AFM micrographs with ten monolayers for 2b and 4b films, respectively.
Figure 15
Figure 15
Small-angle X-ray scattering of a 10-layer Langmuir–Blodgett film of 2b complex: a—four days and b—12 months, after deposition.

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