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Materials Chemistry C
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solutions of nanoparticles with a spin transition around room temperature. The introduction of a chiral anion
DOI: 10.1039/c5tc00161g
properties that are dierent in high and low spin states. We also illustrate here an eect of the chiral
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memory which is caused by the hysteretic spin transition. In addition, a bistable chiral composite
supramolecular system a [Fe(NH2trz)3](L-CSA)2CHCl3 gel is described here.
to the coordination framework makes these nanoparticles display specific chiro-optical (circular dichroism)
Introduction
Chirality, which is an important phenomenon in biology,
physics and chemistry, plays a crucial role in many photonic
experiments.1 This eect of molecular asymmetry is well studied
for organic and biological materials, whereas it is less reviewed
for inorganic and coordination materials, for nanoobjects.2
Nevertheless, a strong chiro-optical response from the interaction of light with chiral plasmonic nanostructures is attracting
much attention. Such nanostructures can be used to enhance
the chiro-optical signal of chiral molecules and can also significantly increase the enantiomeric excess of direct asymmetric
synthesis and catalysis.3 These eects oer numerous implications for biological systems.4 Magnetic chiral colloids that
can rapidly self-assemble into a variety of isomeric forms have
been proposed.5 Various chiral nanoparticles of inorganic semiconductors can be obtained with diverse characteristics of chirooptical activity and excitonic resonance.6
Chiral switches that can be triggered with dierent external
stimuli oer fascinating opportunities as elements in molecular
a
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Fig. 1 Structure and morphology of nanoparticles 1. (a) Schematic representation of a typical Fe(II) 1,2,4-triazole complex structure. Fe(II) ions
are known to form 1D-chains with 4-amino-1,2,4-triazole,36 whereas
anions are situated in the inter-chain channels. (b) DLS measurements
on the colloidal solution of nanoparticles 1. Size distribution is given as
the percent of nanoparticles (distribution by number) from 3 dierent
measurements (298 K). (c) TEM image of nanoparticles 1. (d) Distribution of
nanoparticles by size from the TEM image.
Published on 07 April 2015. Downloaded by Johannes Gutenberg Universitaet Mainz on 17/08/2015 15:25:06.
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Published on 07 April 2015. Downloaded by Johannes Gutenberg Universitaet Mainz on 17/08/2015 15:25:06.
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Conclusions
In conclusion, here we oer a pathway to monodisperse, additivefree and stable colloids of SCO nanoparticles, which can be
versatile for many SCO complexes from a wide family of Fe(II)
1,2,4-triazole compounds. This can provide a route towards dierent SCO nanoparticles with a defined temperature, abruptness and
hysteresis of spin transition. Moreover, not only the chiral anions
but also the chiral ligands can be used when constructing chiral
SCO complexes. The good stability of the presented thermoswitchable chiral nanoparticles in volatile organic solvents can permit
their future processing to thin layers, patterns and nanostructures.
A drastic change of chiro-optical properties with SCO can make
these materials attractive candidates for active elements of photonic
devices operating in the UV and visible regions. The eect of chiral
memory, especially where it appears around biologically relevant
temperatures, may also find applications in dierent experiments.
Experimental
Synthetic procedures
Iron(II) L-camphorsulfonate hexahydrate Fe(L-CSA)26H2O. The
Fe(L-CSA)26H2O salt was synthesised by a procedure similar to
that proposed by D. Coucouvanis for Fe(OTs)26H2O.39 Metallic
iron powder (100 mg, 1.79 mmol, 1.67 equiv.) was added portionwise to the solution of L-camphorsulfonic acid (500 mg, 2.16 mmol,
1 equiv.) in water (2 mL). This mixture was refluxed for 5 h.
Unreacted iron powder was filtered o and the filtrate was left to
crystallize as it cooled. Green crystals of Fe(L-CSA)26H2O were
separated by filtration and dried in air. Yield 487 mg (72%). Anal.
calcd for C20H42FeO14S2: C, 38.34; H, 6.76. Found: C, 38.42; H, 6.84.
IR (KBr): 536, 613, 1054, 1173, 1738, 2984, 2962, 3435 cm 1.
Nanoparticles of [Fe(NH2trz)3](L-CSA)2 in acetonitrile (1). Two
distinct solutions were prepared: (a) iron(II) camphorsulfonate
hexahydrate (10 mg, 0.016 mmol, 1 equiv.) in DMSO (125 mL),
then 2 mL of acetonitrile were added; (b) 4-amino-1,2,4-triazole
(10 mg, 0.119 mmol, 2.5 equiv.) in DMSO (125 mL), then 2 mL
of acetonitrile were added. The two solutions were rapidly
mixed and the mixture turned into a turbid pink colloid of
nanoparticles within a few minutes. The nanoparticles were
separated by centrifugation (20 min, 9000 rpm) and washed
with acetonitrile. They could be dried in air or redispersed in
acetonitrile depending on further experiments. Anal. calcd for
C26H42FeN12O8S2: C, 40.52; H, 5.49; N, 21.81. Found: C, 40.33;
H, 5.57; N, 21.73. IR (KBr): 509, 528, 600, 623, 1043, 1097, 1170,
1195, 1229, 1636, 1745, 2956, 3124, 3277, 3460 cm 1.
Gel of [Fe(NH2trz)3](L-CSA)2 in chloroform (2). All solvents
were thermalized at 293 K. Two distinct solutions were prepared:
(a) iron(II) camphorsulfonate hexahydrate (10 mg, 0.016 mmol,
1 equiv.) in DMSO (125 mL), then 2 mL of chloroform were
added; (b) 4-amino-1,2,4-triazole (10 mg, 0.119 mmol, 2.5 equiv.)
in DMSO (125 mL), then 2 mL of chloroform were added. The two
solutions were rapidly mixed and the mixture turned into a very
viscous pink gel within 1 h.
Physical measurements
UV-Vis measurements. UV/Vis absorbance spectra were recorded
on a Cary 50 spectrophotometer that was equipped with a
thermostated cell holder. The temperature was changed at a
rate of 2 K min 1. When following a MLCT band, the mother
solution of nanoparticles was diluted 1000 times.
CD measurements. CD spectra were recorded on a Jasco J715
CD spectrometer that was equipped with a thermostated cell
holder. The temperature was changed at a rate of 2 K min 1.
Samples were thermalized prior to every measurement for 3 min.
Data were processed using JASCO software.
Magnetic susceptibility measurements. Temperature-dependent
magnetic susceptibility measurements were carried out with a
Quantum-Design MPMS-XL-5 SQUID magnetometer equipped with
a 5 T magnet over the temperature range 2370 K with a cooling
and heating rate of 2 K min 1, and a magnetic field of 0.5 T.
Diamagnetic correction for the molecule (0.000385 emu mol 1)
was applied.
ssbauer measurements. Mo
ssbauer spectra were recorded
Mo
with a 57Co source embedded in a rhodium matrix using a
ssbauer spectrometer equipped with a heating oven.
Wissel Mo
Isomer shifts are given relative to iron metal at ambient
temperature. Simulations of the experimental data were performed with Recoil software.
Transmission electron microscopy. Particle size was determined
by using a SELMI TEM-125K transmission electron microscope.
TEM samples were prepared by placing a droplet (10 mL) of colloid
1 in acetonitrile on a carbon coated copper grid. TEM microphotographs were processed with ImageJ software.
Dynamic light scattering. DLS measurements were performed on
the colloid of nanoparticles in acetonitrile with a Malvern Zetasizer
Nano ZS and processed using standard Malvern Zetasizer software.
Acknowledgements
We acknowledge Olesia I. Kucheriv for assistance with some
synthetic work and for some useful comments on the manuscript.
We also acknowledge Wojciech Nowak for assistance with CD
measurements and Inna V. Vasylenko for TEM experiments.
Published on 07 April 2015. Downloaded by Johannes Gutenberg Universitaet Mainz on 17/08/2015 15:25:06.
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