Synthesis, structures and properties of two novel charge-transfer complexes with the ratio of ferrocenyl:POM of 1:1, (Bu 4N)[CpFeCpCH 2N(C 2H 5) 3][M 6O 19] (M = Mo, W)

• Published in: Solid state sciences Vol. 12; no. 8; pp. 1332 - 1336
• Main Authors: Xu, Haisheng, Zhang, Lei, Li, Zuoxi, Liu, Xuemei, Hu, Huaiming, Xue, Ganglin
• Format: Journal Article
• Language: English
• Published: Issy-les-Moulineaux Elsevier Masson SAS 01-08-2010; Elsevier Masson
• Subjects: Acetal resins; Band spectra; Cationic; Charge-transfer salts; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Cross-disciplinary physics: materials science; rheology; Diffusion; Exact sciences and technology; Ferrocene; Fullerenes and related materials; Growth from solutions; Infrared and raman spectra and scattering; Materials science; Methods of crystal growth; physics of crystal growth; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Other materials; Physics; Polyoxometalates; Reflectance; Reflectivity; Solid state; Specific materials; Spectroscopy; Spectrum properties; Structure; Visible and ultraviolet spectra; X-rays; Polyoxometalates; Structure; Spectrum properties; Charge-transfer salts; Ferrocene; Metallates; Space groups; Diffuse reflection; Organometallic compounds; Fluorescence; XRD; Infrared spectra; Monoclinic lattices; Molybdenum; Solid state; Reflection spectrum; Acceptor center; Crystal growth from solutions; Ultraviolet visible spectrum; Donor center; Charge transfer complexes; Crystal structure
• ISSN: 1293-2558; 1873-3085
• DOI: 10.1016/j.solidstatesciences.2010.05.002

The first charge-transfer (CT) complexes containing the cationic ferrocenyl donor CpFeCpCH
2N
+(C
2H
5)
3 and polyoxometalate (POM) acceptors of the Lindqvist structural type [M
6O
19]
2− (M=Mo, W) with the ratio of ferrocenyl:POM of 1:1, (Bu
4N)[CpFeCpCH
2N(C
2H
5)
3][Mo
6O
19] (
1) and (Bu
4N)[CpFeCpCH
2N(C
2H
5)
3][W
6O
19] (
2), were synthesized in high yields (67–71%) by traditional solution synthetic method, and characterized by elemental analysis, IR spectroscopy, UV–vis diffuse reflectance spectrum, luminescent spectrum and single crystal X-ray diffraction. The X-ray structure of the two novel CTCs were both solved in the monoclinic space group
P2
1/
n and show the close interaction of the hydrogen atoms of the CpFeCpCH
2N
+(C
2H
5)
3 with the oxygen atoms on the surface of the POM. The UV–vis diffuse reflectance spectrum in the solid state indicates the presence of a new CT band at
λ
max
=
576
nm and 590
nm for
1 and
2, respectively, attributed to CT transitions between the ferrocenyl donors and the POM acceptors. The luminescent spectroscopy of
1 exhibits the weakened fluorescence signals compared to that of the corresponding POM and the cationic donor, however,
2 has an intense emission at about
ca. 394
nm and may be excellent candidates for potential solid-state photofunctional materials.
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