Synthesis, structure and properties of the first hybrid Bi 2Cl93- supramolecular compound based on macrocyclic rotator-stator assembly

Article abstract of DOI:10.1016/j.inoche.2012.05.015

The first hybrid Bi(III) supramolecular compound based on organic ammonium and 18-crown-6, [(4-FBNH₃)₃·(18-crown-6) ₃·(Bi₂Cl₉)] (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRPD and ¹H NMR (4-FBNH₃ = 4-fluorobenzenaminium). The Bi(III) centers were chelated through three μ₂-Cl donors to form a macro-anion (Bi₂Cl₉)^3- unit. And the rotator-stator assembly, [(4-FBNH₃)·(18-crown-6)]⁺, was formed by the 4-FBNH₃⁺ cation inserting into the crown ether through strong NH...O H-bonding interactions. The large anions and rotator-stator cations were alternately stacked together to build the supramolecular functional compound. In addition, the thermal analysis and luminescent properties were investigated.

Full text of DOI:10.1016/j.inoche.2012.05.015

Inorganic Chemistry Communications 22 (2012) 29–32
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Synthesis, structure and properties of the first hybrid Bi Cl 93 supramolecular
−
2
compound based on macrocyclic rotator-stator assembly
Yan-Hong Peng ⁎, Shao-Fa Sun
School of Nuclear Technology, Chemistry and Biology, Hubei University of Science and Technology, Xianning 437100, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The first hybrid Bi(III) supramolecular compound based on organic ammonium and 18-crown-6, [(4-FBNH ) ·
3
3
Received 9 January 2012
Accepted 4 May 2012
Available online 14 May 2012
(
18-crown-6)
analysis, IR, XRPD and H NMR (4-FBNH
three μ
18-crown-6)] , was formed by the 4-FBNH
3 2 9
·(Bi Cl )] (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental
1
3
=4-fluorobenzenaminium). The Bi(III) centers were chelated through
3−
2
-Cl donors to form a macro-anion (Bi
2
Cl
9
)
3
unit. And the rotator-stator assembly, [(4-FBNH )·
+
+
(
3
cation inserting into the crown ether through strong
Keywords:
N\H…O H-bonding interactions. The large anions and rotator-stator cations were alternately stacked to-
gether to build the supramolecular functional compound. In addition, the thermal analysis and luminescent
properties were investigated.
Bi(III) complex
Crystal structure
Fluorescence
Rotator-stator assembly
Macrocycle
© 2012 Elsevier B.V. All rights reserved.
Multiform weak intermolecular interactions, such as hydrogen-
bonding, charge-transfer and van der Waals forces, can be used to con-
struct supramolecular structures. It is easy to realize the higher selec-
tivity in molecular recognitions if the host molecules and the guest
species were combined together by the above intermolecular forces,
when the host molecules possess some specific groups that can bind
the guests by distinctive effect. Hereby, it may be possible to obtain op-
timum molecular self-assembly structures through the designed
modes of intermolecular interactions [1–3]. Therefore, it is interesting
to construct the functional materials for its potential applicability in
fields of mediated ion transport, molecular recognition [4], self-
assembly engineering [5], luminescence and anion-activated catalysis
(multichloro-metal ion, heteropolyanion) can result in the formation
of multiple composites through regulating the stacking, because there
should be the same number of cations to keep the charge balance.
3−
+
For example, one Bi
and then three Ar-NH
2
Cl
9
is equivalent with three Ar-NH
are combined with three 18-crown-6 (18-
3
cations,
+
3
crown-6 can show the highest affinity with organic ammonium cations
by adopting a 1:1 stoichiometry in most cases [6,13]). In this way, the
multi-component compound was formed. In addition, the crown
ether can encapsulate or contain the cations via three (or six) strong
Ar–N–H…Omacrocycle H-bonding interactions. And nearly all the Ar–N
bonds of the cations are almost perpendicular to each mean plane of
the crown ether rings. This rotator-stator mode allows the cations
[
6]. The molecular rotation has attracted much attention with respect
can rotate freely, leading to the structural diversity of the [(Ar-
+
to the development of artificial molecular motors, in an attempt to im-
itate the intelligent and useful functions of biological molecular motors.
Recently, a large number of novel supramolecular structures based
on 18-crown-6 macrocyclic ether have been isolated [7–12], in which
the interplay of various types of intermolecular interactions takes
important role in the complexation process. The macrocycle has six –
NH
3
)·(18-crown-6)] . For the above features and synthesis strategies,
3−
the aromatic ammonium, Bi
2
Cl
9
and 18-crown-6 were selected to
build the supramolecular structure. In the present investigation, we
reported the synthesis, structure and properties of the title compound,
3 3 3 2 9
[(4-FBNH ) ·(18-crown-6) ·(Bi Cl )] (1) [14]. The compound 1 is the
first hybrid Bi(III) supramolecular compound based on macro [(Ar-
+
O-CH
the crown ether can be free-form deformation. For this reason, the
8-crown-6 is a good host to include the guest ammonium ions
2 2
-CH -O– repeating units, which is natural flexibility. Thereby,
NH
3
)·(18-crown-6)] assembly.
The structure of 1 was identified by satisfactory elemental analysis,
1
(
IR and X-ray diffraction [15,16]. The IR spectra shown a series of strong
+
+
+
−1
−NH
4
, R-NH
3
and Ar-NH
3
) by adjusting their cavity sizes. Further-
peaks at 1593, 1483, 1208, 778 and 704 cm , those peaks are the char-
acteristic of aromatic ring [17]. Moreover, the sharp peak at 3087 cm−
1
more, the types of the anions and ammonium cations also can affect
the stoichiometry and molecular conformation of these host–guest
inclusion complexes. The high charge number and macro anions
corresponds to the aromatic H atoms. The broad band around
−
1
3400 cm
suggests that the nitrogen atoms of the ligands were pro-
tonated to form the H-bonds. The strong double peaks at 2916 and
−
1
2
855 cm are attributed to the νas(C-H) and ν
s
(C-H) of methylene, re-
spectively. The characteristic peaks of crown ether are presented at
1403, 1291, 1223 and 1090 cm . X-ray powder diffraction (XRPD)
⁎
Corresponding authors. Tel./fax: +86 715 8338072.
E-mail address: chempengh@yahoo.com.cn (Y-H. Peng).
−
1
1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2012.05.015

30
Y-H. Peng, S-F. Sun / Inorganic Chemistry Communications 22 (2012) 29–32
stator assemblies with 18-crown-6 rings, via strong hydrogen-bonding
interactions resulting in the formation of three macro-cation [(4-
+
+
3 3
FBNH )·(18-crown-6)] units. The –NH moieties interact with the six
oxygen atoms of crown ether rings through three short linear N–H···O
H-bonds and three longer acute interactions. The distances between the
N atoms and the O atoms in the crown ether are also short, indicating di-
polar donor-accepter attractions (H-bonding interactions) [the N…O
distances are 2.849(5), 2.937(6), 2.831(5), 3.013(5), 2.845(5) and
2
.875(5) Å for N1; 2.828(6), 2.950(6), 2.870(6), 2.932(6), 2.887(6)
and 2.852(5) for N2; 2.949(7), 2.856(7), 2.991(8), 2.944(7),
.819(7) and2.945(7) Å for N3, respectively] (Table 1). The conforma-
Å
2
tion of the crown ether rings and the hydrogen-bond geometry in the
assemblies closely resemble those in related adducts of 18-crown-6
and primary alkylammonium salts [8]. The three macrocycles adopt a
conformation with approximate C3v symmetry, with all O–C–C–O tor-
sion angles being gauche and alternating in sign, and all C–O–C–C torsion
angles being trans. The O atoms of each crown ether ring are nearly co-
planar, for ring1: the O1, O3 and O4 are located above the mean plane of
Fig. 1. The XRPD curve for compound 1.
Ocrown ring (O1 to O6 ), and O2, O5 and O6 atoms below the plane; for the
ring 2: the O7, O9 and O11 (O8, O10 and O12) are located above and
below the mean plane of Ocrown ring (O7 to O12 ); for the ring 3: the
O13, O15, O16 and O18 (O14 and O17) are located above and below
the mean plane of Ocrown ring (O13 to O18 ), with average deviations of
the O atoms from the Ocrown ring planes of 0.2246, 0.5457 and 0.3330
for the three rings, respectively. In addition, the C–N(1), C–N(2) and
+
C–N(3) bonds of the 4-FBNH
3
cations are almost perpendicular to
each mean plane of the crown ether. And the N1, N2 and N3 atoms of
the cations are out of each plane with 0.984(3)Å, 0.796(3)Å and
3
−
1
.011(5)Å, respectively. The Bi
ions to the supramolecular [(4-FBNH
the six-coordinate Bi(III) centers adopt irregular octahedral geometry
composed of three μ -chelated chloride atoms and three terminal
chloride atoms. And the μ -chelated Cl atoms (Cl4, Cl5 and Cl6) bridged
the mental ions into a binuclear Bi Cl unit, with the Bi\Cl bond
Cl
2 9
anions are presented as counter-
+
3
)·(18-crown-6)] cations. Both
2
2
2
3
Fig. 2. The CD and UV/Vis spectra for compound 1.
distances in the range of 2.830(2)–2.980(2) Å, and Cl\Bi\Cl bond
angles in the range of 83.30(4)-84.02(4)°. Uniquely, there are three
+
[
(4-FBNH
3
)·(18-crown-6)]
rotator-stator assemblies within the
analysis: The agreement between the experimental and simulated
XRPD patterns indicated the phase purity of 1 (Fig. 1). The difference
in reflection intensities between the simulated and experimental pat-
terns was mainly due to the different powder size during collection of
the experimental XRPD data. The CD and corresponding UV/Vis spectra
of the complex were measured in the solid state at room temperature
asymmetric unit, which possess the similar binding mode. This may be
3−
caused by the trivalent Bi Cl9 anion, which is relatively larger than
2
the other common anions. This is very similar to the known [Ni(dmit) ]ˉ
2
4
3−
and [PMo12O40] ˉ anions [11,12]. So the Bi Cl can be embedded into
large and structurally diverse [(4-FBNH )·(18-crown-6)] cations to re-
2
9
+
3
sult in the supramolecular structure (as shown in Fig. 4a and b).
(
Fig. 2). The UV/Vis spectrum of the complex 1 exhibit an absorption
The thermal behavior of the title compound 1 was investigated from
20 to 700 °C. The DSC and TGA curves are shown in Fig. 5. For the DSC
curve, there are three thermal anomaly peaks, one intense endothermic
peak and two continuously exothermic peaks. The first endothermic
stage occurs in the range of 278 to 293 °C with the peak temperature
at 286 °C, which proves that the compound has been melted during
this temperature range. The first exothermic anomaly indicates the de-
composition of the organic parts with the peak value at 332 °C.
The second broad exothermic peak was continuous with the previous
one, which has a very broad range of 100 °C. In the TG diagram of 1,
[(4-FBNH ) ·(18-crown-6) ·(Bi Cl )], the two main steps of weight
bands at the range of 200–400 nm, and the corresponding CD curve
shows a series of chiral characteristic peaks of compound 1. The above
spectral analyses are in agreement with the determined single-crystal
structure (Scheme 1).
Single-crystal X-ray analysis reveals that complex 1 crystallized in
1 1 1
the orthorhombic space group P2 2 2 . The asymmetric unit contains
nine Cl anions, two Bi(III) cations, three 4-FBNH
1
were protonated to form the –NH
crystallorgraphically independent 4-FBNH
−
+
3
cations and three
molecules
H-bonding donors. Then the
8-crown-6 molecules (Fig. 3). All the three 4-FBNH
2
+
3
+
3
cations joined the rotator-
3
3
3
2
9
Scheme 1. Synthesis process and H-bonding modes of compound 1.

Y-H. Peng, S-F. Sun / Inorganic Chemistry Communications 22 (2012) 29–32
31
Fig. 3. Viewing of the asymmetric unit and showing the coordination environment in
complex 1 with the displacement ellipsoids at the 30% probability level.
losses were observed in the temperature range from room temperature
to 700 °C. The first step occurs in the range of 290 to 385 °C, amounting
to about 59.7% weight loss and corresponding to the escape of all organ-
ic molecules (calculated 60.5%). Then, the second weight loss appeared.
The total observed weight loss at 700 °C is 65.9%, and the final presum-
3
ably residual is BiCl . The two decomposition-temperature stages are
within the ranges of 290–385 °C and 390–550 °C, respectively. This is
the typical features for hybrid rotator-stator compounds based on 18-
crown-6.
2
The fluorescent properties of the complex 1 and 4-FBNH were in-
vestigated at room temperature in the solid state. The intense broad
emission band at 387 nm was observed for compound 1 upon excita-
tion at λ=320 nm, as illustrated in Fig. 6. Moreover, the free 4-
FBNH
under the same experimental conditions. The emission of complex 1
is red-shifted about 6 nm compared to that of free ligand 4-FBNH . Ob-
viously, the emissions derived from the conjugated systems of the aro-
matic amine molecules. After coordination, the –NH groups of
fluoroaniline molecules were protonated, and the arm-like –NH
2
presents a weak photoluminescence emission at 381 nm
2
2
+
3
Fig. 4. The self-assembly packing of the rotator-stator [(4-FBNH
3
)·(18-crown-6)]+ and
groups were firmly bound in the crown ether rings through six strong
N\H…O H-bonding interactions, then the parent aromatic rings have
3−
(Bi
2
Cl
9
)
anion units viewed along the b-axis (Fig. 4a) and c-axis (Fig. 4b). Hydrogen
atoms are excluded for clarity.
been fixed and shown a better plane conjugacy. Meanwhile, the –
+
NH
3
group was involved in the conjugated effect of seven centers
with one electron to result in the formation of a new and larger conju-
gated system (benzene ring and one amino N atom). Therefore, the ri-
gidity and the conjugated effect of this aromatic system have been
promoted during the molecular packing, which plays the main role to
the luminescence intensity and red-shift effect. Thus, the compound 1
and the 4-FBNH have shown different luminescence properties.
2
In summary, the ether-based macrocyclic supramolecular structure
has been synthesized successfully by connecting the organic ammonium
and 18-crown-6 as the cation assemblies, and the polyhedral metal
chloride as trivalent macro anions. In this way, the large supramolecular
+
cations, [(4-FBNH
3
)·(18-crown-6)] , were introduced into the crystal
Table 1
+
material, which is comprised of the 4-FBNH
3
and 18-crown-6 via
Hydrogen bonds data for compound 1.
D-H…A
d(D-H)
d(H…A)
d(D…A)
b(DHA)
N2-H2C…O6_$1
N2-H2C…O1_$1
N2-H2D…O2_$1
N2-H2D…O3_$1
N2-H2E…O4_$1
N2-H2E…O5_$1
N1-H1C…O10_$2
N1-H1C…O11_$2
N1-H1D…O12_$2
N1-H1D…O7_$2
N1-H1E…O8_$2
N1-H1E…O9_$2
N3-H3C…O15
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
2.03
2.28
2.10
2.25
2.09
2.20
2.16
2.19
2.07
2.36
2.05
2.28
2.14
2.20
2.17
2.29
2.18
2.20
2.828(6)
2.950(6)
2.870(6)
2.932(6)
2.887(6)
2.852(5)
2.849(5)
2.937(6)
2.831(5)
3.013(5)
2.845(5)
2.875(5)
2.949(7)
2.856(7)
2.991(8)
2.944(7)
2.819(7)
2.945(7)
149.1
131.5
145.0
133.3
148.6
130.1
133.8
140.5
143.3
130.4
148.2
124.1
150.6
130.5
152.5
130.0
128.7
141.5
N3-H3C…O14
N3-H3D…O13
N3-H3D…O18
N3-H3E…O16
N3-H3E…O17
Symmetry codes: $1 1/2−x, −y, 1/2+z $2−x, 1/2+y, 1/2−z.
Fig. 5. The DSC and TGA curves for compound 1.

32
Y-H. Peng, S-F. Sun / Inorganic Chemistry Communications 22 (2012) 29–32
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2
Fig. 6. Fluorescent emission spectra of compound 1 and free 4-FBNH .
H-bonding interactions between the cavity-O and the Ar-NH
3
+. The de-
tails about the synthesis, crystal structure, IR, UV, 1HNMR, TGA, DSC
and fluorescence properties of the inclusion compound 1 have been dis-
cussed. This approach allows us to modulate the structural assemblies,
thus many multifunctional rotator-stator compounds with useful prop-
erties will be obtained.
[
10] T. Akutagawa, D. Sato, H. Koshinaka, M. Aonuma, S. Noro, S. Takeda, T. Nakamura,
Solid-state molecular rotators of anilinium and adamantylammonium in
[
Ni(dmit)(2)](−) salts with diverse magnetic properties, Inorg. Chem. 47 (2008)
5951–5962.
[11] T. Akutagawa, D. Endo, F. Kudo, S.I. Noro, S. Takeda, L. Cronin, T. Nakamura, A solid-
state supramolecular rotator assembled front a Cs-crown ether polyoxometalate hy-
brid: (Cs+)(3)([18]crown-6)(3)(H+)(2)[PMo12
O40], Cryst. Growth Des. 8 (2008)
812–816.
Acknowledgments
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4−
phenylenediamine-crown ether -[PMo12
628–8637.
O
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]
salts, Inorg. Chem. 45 (2006)
8
This work was financially supported by the Provincial Department
of Education (Q20112802) of Hubei Province, Start-up foundation of
Hubei University of Science and Technology (KB1008), the National
Natural Science Foundation and Hubei Province NSF (2011CDC137,
[
[
13] H.J. Buschmann, L. Mutihac, K. Jansen, Complexation of some amine compounds
by macrocyclic receptors, J. Incl. Phenom. Macrocycl. Chem. 39 (2001) 1–11.
14] Compound 1 was synthesized by employing mild solvothermal method in the
presence of organic amine, BiCl
.26 g) was added into an 20 mL H
ume ratio=5 : 2 : 5 : 1) under constant stirring. To this solution, 0.66 g (6 mmol)
of 4-FBNH was slowly added. Finally, 1.58 g (6 mmol) of 18-crown-6 and addi-
3
, 18-crown-6 and dilute HCL. BiCl
3
(4 mmol,
1
2
O / DMF / MeOH / HCl mixture solvent (vol-
2
010CDZ048).
2
tional 1 mL of HCl (36%) were added into the mixture, and the mixture was
stirred for 1 h to obtain a homogeneous gel. The final mixture with the molar
Appendix A. Supplementary material
composition of BiCl
3 2
/ 18-crown-6 / 4-FBNH (2 : 3 : 3) was transferred into a
2
5 mL Teflon-lined acid digestion bomb and heated at 100 °C for 2 days under au-
CCDC-859160 for 1 contains the supplementary crystallographic
data for this paper. The data can be obtained free of charge from the
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article can
be found, in the online version, at http://dx.doi.org/10.1016/j.inoche.
togenous pressure. Then the reaction was slowly cooled to room temperature at a
rate of 5 °C/h. Colorless block monophasic crystals suitable for X-ray diffraction
were obtained in 51% yield (based on BiCl ). H NMR (300 MHz, DMF, TMS,
1
3
298 K): δ (ppm): 8.62 (d, 2 H, aromatic-H), 8.44 (d, 2 H, aromatic-H) and 3.43
(
(
d, 24 H, methylene-H). Elemental analysis for 1,
54 2 9 3 3 18
C H93Bi Cl F N O
1866.32): Anal. (%) calcd. C 34.72, H 4.98, N 2.25; found C 34.59, H 4.87, N
2
012.05.015.
2.19. IR spectrum (cm−1, KBr): 3423(m), 3401(s), 3389 (m), 3087(w), 2916(s),
2
1
6
855(s), 1593(m), 1570(w), 1483(m), 1403(s), 1374(w), 1291(s), 1223(m),
208(m), 1090(s), 1044(w), 927(s), 872(w), 825(w), 778(m), 730(w), 704(m),
48(w), 569(w), 538(w), 502(w).
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