Synthesis and Crystal Structure of a New Charge-Transfer Complex
[(C
19
H
18
N
3
)
2
H][PMo
12
O
40
]
Guang Liu, Qi Li, and Shi-Wei Zhang*
Beijing/P. R. China, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular
Engineering of Peking University
Received March 25th, 2002.
Abstract. A new charge-transfer complex with tri-(p-aminophenyl)-
carbonium cations was synthesized from the hydrothermal reaction
of pararosanilin and (NH
4
)
3
[PMo
12
O
40
]·3H
2
O, and was charac-
terized with UV-vis, EPR and elemental analysis, as well as single
crystal x-ray diffraction.
Synthese und Kristallstruktur des neuen Charge-Transfer-Komplexes
[(C
19
H
18
N
3
)
2
H][PMo
12
O
40
]
Inhaltsübersicht. Durch hydrothermale Reaktion von Pararosanilin
mit (NH
4
)
3
[Pmo
12
O
40
]·3H
2
O wurde ein neuer Charge-Transfer-
Komplex mit Tri(p-aminophenyl)carbonium-Kationen synthetisiert
1 Introduction
Metal oxide clusters of polyoxometalates (POMs) have at-
tracted great attention in recent years due to their versatility
and utility in catalysis (e.g., photochemical dehydrogen-
ations of organic substrates), medicine (e.g., anti-viral and
anti-tumor drugs), and material sciences [1]. Of particular
interest is the use of POMs as electron-accepting moieties
in charge-transfer materials that are prepared by cocrystalli-
zation with organic donors [2]. This usage is based on (i) the
good solubility of POMs in both aqueous and nonaqueous
solutions, (ii) the possibility of varying the charges, shapes,
and sizes of POMs that can induce new donor packings
and, therefore, new band structures, (iii) the ability of
POMs to act as electron reservoirs and (iv) the possibility
of introducing magnetically active transition metal ions at
specific sites of the POMs [3]. Some charge-transfer com-
plexes of this class have been reported to show interesting
metallic behavior, such as [ET]
5
[VW
5
O
19
]·5H
2
O [4] and
[ET]
11
[P
2
W
18
O
62
]·3H
2
O [5] (ET⫽bis(ethylenedithio)tetra-
thiafulvalene). Donors in those charge-transfer complexes
include substituted amides [6], aromatic amines [7] and elec-
tron-rich substrates such as tetrathiafulvenes (TTF) [3], de-
camethyferrocene [3] and so on. All these donors have
* Prof. S. W. Zhang
College of Chemistry and Molecular Engineering,
Peking University,
Beijing 100871, P. R. China.
Fax number: (8610) 62751725
E-mail: zsw@chem.pku.edu.cn,
Z. Anorg. Allg. Chem. 2002, 628, 1895⫺1898 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/1895⫺1898 $ 20.00⫹.50/0 1895
Keywords: Charge-transfer complex; Keggin structure; Pararos-
anilin; crystal structure; EPR spectrum
und charakterisiert mittels UV-VIS-, EPR-Spektroskopie und Ele-
mentaranalyse sowie durch Einkristall-Röntgenbeugung.
planar conjugated π systems, which can stabilize the posi-
tive charge and reduce energy band gap. Many organic dyes,
such as pararosanilin, methylviolet and malachite green,
have a basic structure of triphenylcarbon group. This struc-
ture has a large planar conjugated π system and plenty of
reactive sites that can be modified by functional groups. On
the other hand, the flamboyant colors of these dyes show
the potential electric and optic properties. But so far, no
charge-transfer complex containing such dye donor has
been reported. Here we report the synthesis and charac-
terization of a new complex with dye cations of tri--
(p-aminophenyl)carbonium and Keggin type polyanions.
2 Experimental
2.1 Preparation
[(C
19
H
18
N
3
)
2
H][PMo
12
O
40
](1) was synthesized by the hydrother-
mal reaction of 0.16g (0.49 mmol) pararosanilin and 0.48g
(0.25 mmol) (NH
4
)
3
[PMo
12
O
40
]·3H
2
O in 15ml (0.83 mol) water at
180 °C for 3 days. Black crystals were filtered from blue solution,
washed with water and dried in air. Weight 0.23 g, yield 38 %.
Elemental analysis: C
38
H
37
Mo
12
N
6
O
40
P
1
(Mr ⫽ 2400), C 19.1
(calc. 19.0); H 1.49 (1.54); Mo 47.8 (48.0); N 3.53 (3.50); P 1.32
(1.29) %.
2.2 X-ray crystallographic study
A blue block single crystal with dimensions 0.25mm ⫻ 0.12mm ⫻
0.10mm was mounted on a Rigaku RAXIS-RAPID X-ray dif-
fractometer. Diffraction data was collected at 173K with graphite
monochromated MoKα radiation (λ ⫽ 0.071073nm) operating at
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