Preparation and characterization of 4-[4-(dimethylamino )styrl]-1-methyl-pyridinium lead triiodide and its tribromide analog

Article abstract of DOI:10.1515/znb-2001-0214

Using 4-[4-(dimethylamino)styryl]-1-methyl-pyridinium iodide, lead iodide, tetrabutylammonium bromide and lead bromide as starting materials, the title compounds were prepared and characterized analytically and spectroscopically.

Full text of DOI:10.1515/znb-2001-0214

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dine as catalyst [5-6]. The bromide analog
(DSM B) was obtained by treating DSMI with
NaBr in acetonitrile followed by recrystallization
from methanol.
Preparation and Characterization of
4-[4-(Dimethylamino)styryl]-l-methyl-
pyridinium Lead Triiodide and its
Tribromide Analog
Compound 1 was prepared as follows: A hot so-
lution of DSMI (73.2 mg, 0.2 mmol) and Bu4NI
(300 mg) in CH 3CN (10 ml) was mixed with a hot
solution of Pbl2 (92.2 mg, 0.2 mmol) and Bu4NI
(300 mg) in CH 3CN (10 ml). A fter slow cooling to
room tem perature a red microcrystalline precipi-
tate was obtained filtered, washed with acetone
and air dried; yield 106 mg (64%). Analysis for
C16H 19N2I3Pb (827): calcd. C 23.22, H 2.30, N 3.38,
I 46.07; found C 23.32, H 2.20, N 3.35, I 46.22.
Compound 2 was prepared as follows: A hot so-
lution of DSMI (73.2 mg, 0.2 mmol) and Bu4NBr
(161 mg, 0.5 mmol) in CH3CN (25 ml) was mixed
with a hot solution of PbBr2 (73.4 mg, 0.2 mmol)
and Bu4NBr (161 mg, 0.5 mmol) in CH3CN (25
ml). A fter slow cooling to room tem perature, a
precipitate of small brown-golden elongated plates
was obtained; it was filtered, washed with acetone
and air dried; yield 91 mg (66%). Analysis for
C 16H 19N2Br3Pb (686): calcd. C 27.99, H 2.77,
N 4.08, Br 34.98; found C 28.12, H 2.87, N 3.93,
Br 35.02.
G. C. Papavassiliou, G. A. Mousdis,
and I. B. Koutselas
Theoretical and Physical Chemistry Institute,
National Hellenic Research Foundation,
48, Vassileos Constantinou Ave., Athens 116/35,
Greece
Reprint requests to Prof. G. C. Papavassiliou.
Fax: (301) 7273794
Z. Naturforsch. 56b, 213-214 (2001);
received November 21, 2000
Organic-Inorganic Hybrids, Low-Dimensional
Semiconductors, Optical Properties
Using
4-[4-(dimethylamino)styryl]-l-methyl-
pyridinium iodide, lead iodide, tetrabutylammon-
ium bromide and lead bromide as starting materi-
als, the title compounds were prepared and
characterized analytically and spectroscopically.
Introduction
Organic-inorganic hybrid compounds based on
alkyl ammonium, aryl-alkyl ammonium, the corre-
sponding wo-thiuronium cations and metal halide
anions have been prepared and investigated exten-
sively (see [1-4] and refs therein). In this paper,
the preparation and characterization of two or-
ganic-inorganic hybrid compounds based on
methyl-pyridinium cation and lead halide anions
are reported. These are:
The crystals of the new compounds 1 and 2 were
not good enough for X-ray crystal structure deter-
mination. Thin deposits of compounds on quartz
plates were obtained by rubbing the compounds
on the plates. The optical absorption (OA) and
photoluminescence (PL) spectra were observed by
instrum entation described in [4].
a
Optical Properties and Discussion
Fig. 1 shows the OA and PL spectra of 1 as well
as the OA spectrum of DSMI for comparison. The
OA spectrum of 1 exhibits an excitonic peak at 395
nm, due to the P bl3 network. The stoichiometry of
1 and the position of the excitonic band indicate
that the Pbl3 network is either an infinite twin
chain of edge-sharing Pbl6 octahedra, as in the
case of [Ci0H 7CH 2NH 3]PbI3 [4b,c], or an infinite
chain of face-sharing Pbl6 octahedra, as in the case
of [C5H 12N ]PbI3 [3,9]. The OA spectrum of 1 ex-
hibits a broad charge-transfer band around 486
nm, and the PL spectrum exhibits a band at 671
nm. The intensities and the shapes of the OA and
In these new compounds, both anion [1-3] and
cation [5-8] are photoactive species.
Experimental
rra«s-4-[4-(Dimethylamino)styryl]-l-methyl-
pyridinium iodide (DSMI) was prepared by the re- PL bands do not show considerable differences in
action of 4-dimethylamino-benzaldehyde with 1,4- comparison to those of DSMI.
dimethylpyridinium iodide in ethanol at reflux
tem perature overnight in the presence of piperi-
Fig. 2 shows the OA and PL spectra of 2 as well
as the OA spectrum of DSMB for comparison.
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214
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X(nm)
X (nm)
Fig. 1. OA (a, b) and PL (a\ b') spectra of 1 (a, a') and Fig. 2. Same as Fig. 1, but for 2 (a, a') and DSMB (b, b').
DSMI (b, b'). Excitation 450 nm.
ated DSMI in mica [8] and MPS3 (M = Mn, Cd,
The spectra are similar to 1 and DSMI, respec-
tively, except that the OA of 2 exhibits an exci-
tonic band at 323 nm, due to the PbBr3 network
as in the case of [C5H 12N]PbBr3 [9,10].
Zn) [6]. The intercalation compounds in MnPS3
and CdPS3 exhibit nonlinear optical properties [6].
Similar results are expected for 1 and 2. Moreover,
for 1 and 2 it is expected that the incorporation of
of semiconductor PbX2 (X = I, Br) into the organic
matrix (DSMX) will increase the conductivity. D e-
tails on the optical and related properties of 1 and
In
contrast
to
the
PL
spectra
[C10H 7CH2NH3]PbI3,[C 14H 9CH2SC(NH2)2]2PbBr4
and similar compounds (see [4] and refs therein),
the PL spectra of 1 and 2 do not indicate any en- 2 as well as the preparation and the properties of
ergy transfer from the excitonic states of the inor- similar organic-inorganic hybrids based on stilba-
ganic component to the electronic state of the or- zolium and other chromophores (e.g., those re-
ganic component.
In the region of 400 to 800 nm, the spectra of 1
and 2 are similar to those obtained from intercal-
ported in [6]) and metal halides will be reported
elsewhere.
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