Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand

Article abstract of DOI:10.1039/c6dt01756h

The π-conjugated tetrathiafulvalene (TTF) annulated ligand was introduced into a dicyanometallate for the first time, leading to the synthesis of the versatile redox-active dicyanideferrite building block [(n-Bu)₄N][Fe(TTFbp)(CN)₂] (

Full text of DOI:10.1039/c6dt01756h

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Leong, J. Ru, D. M. D'Alessandro, Y. Song and J. Zuo, Dalton Trans., 2016, DOI: 10.1039/C6DT01756H.
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Chiral Heterobimetallic Chains from a Dicyanideferrite BuilDdOiIn: 10g.1039/C6DT01756H
Block including a π-conjugated TTF Annulated Ligand
Long Cui,† Zhong-peng Lv,† Chanel F. Leong,‡ Jing Ru,† Deanna M. D’Alessandro,‡
You Song,† and Jing-Lin Zuo*†
†
State Key Laboratory of Coordination Chemistry, School of Chemistry and
Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures,
Nanjing University, Nanjing 210093, P. R. China
‡School of Chemistry, The University of Sydney, New South Wales 2006, Australia
ABSTRACT: The π-conjugated tetrathiafulvalene (TTF) annulated ligand was
introduced into dicyanometallate for the first time, leading to the synthesis of the
versatile redox-active dicyanideferrite building block [(n-Bu)4N][Fe(TTFbp)(CN)2]
(H2TTFbp
=
N-(2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-5-(picolinamido)
benzo[d][1,3]dithiol-6-yl) picol inamide). The incorporation of the new ligand with
chiral MnIII Schiff-base complexes resulted in two enantiopure one-dimensional
complexes,
[Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n
(2-(SS))
(2-(RR))
and
=
[Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n
(Salphen
N,N′-1,2-diphenylethylene-bis(salicylideneiminato) dianion), which were synthesized
and structurally characterized. Circular dichroism (CD) and vibrational circular
dichroism (VCD) spectra confirmed the enantiomeric nature of the optically active
complexes, and structural analyses revealed the formation of neutral cyanide-bridged
double chains in 2-(RR) and 2-(SS). Solution and solid state CV studies revealed the
redox-active characteristics of the complexes. Antiferromagnetic couplings were
detected between FeIII and MnIII centers within a chain, and a field-induced magnetic
phase transition was observed (TN = 4.8 K). The introduction of electroactivity and
chirality into cyanide-bridged complexes with interesting magnetic properties leads
the way towards new multifunctional materials.
* To whom correspondence should be addressed. Email: zuojl@nju.edu.cn; Fax: +86-25-83314502.
Nanjing University.
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Introduction
For the last three decades, molecule-based magnetic materials exhibiting intriguing
magnetic behaviors, such as magnetic ordering with high ordering/critical
temperatures (Tc), single-molecule magnets and single-chain magnets, have attracted
significant attention due to their potential applications in memory storage, quantum
computers and spin-based molecular electronics.1 With the ever-increasing demands
for the development of new technologies, the exploration of new materials with
diverse properties is increasing.2 One of the major goals is the generation of magnetic
materials that not only possess expected properties, but also combine two or more
characteristics into a multifunctional system.3
Since the first observation of magneto-chiral dichroism in 1997,4 intense
investigation has been devoted to enantiopure chiral magnets5-7 which are hybrid
materials consisting of natural optical activity and magnetic ordering. In this field, the
class of building blocks known as cyanometallates has been used to prepare chiral
magnetic compounds.8 Several such complexes with controlled structures have been
successfully synthesized by selection of appropriate cyanide building blocks and
unsaturated transition-metal complexes containing chiral ligands.8b,8e
As an organic donor, tetrathiafulvalene (TTF) and its derivatives are well known as
essential building blocks for their strongly electron-donating and attractive reversible
redox properties.9 They have been associated with d or f metal ions to elaborate
multifunctional materials which possess magnetic and electrical properties.10-12 One
effective strategy to achieve a π-d systems is to elaborate a coupling between mobile
and localized electrons through π-conjugated linkages.13 Using this approach, our
group have concentrated significant effort on building molecular systems
incorporating TTF-based ligands to generate subsequent properties such as redox
activity and electronic conductivity.14
With the goal of increasing the functionality of the system, the present work
investigates the introduction of a planar π- conjugated TTF annulated ligand into the
dicyanideferrite building block, [(n-Bu)4N][Fe(TTFbp)(CN)2] (H2TTFbp.=
N-(2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-5-(picolinamido)benzo[d][1,3]dithiol
2

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-6-yl) picol inamide) (Scheme 1), for the first time. Chirality can be introduced into
such systems by using the appropriate chiral ancillary ligand for coordination with
paramagnetic ions. Herein, with the use of the new redox-active dicyanideferrite
building block and enantiopure MnIII precursors including a Schiff-base ligand, two
chiral one-dimensional complexes [Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n (2-(RR))
and
[Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n
(2-(SS))
(Salphen
=
N,N′-1,2-diphenylethylene-bis(salicylideneiminato) dianion), were synthesized. Their
crystal structures, CD spectra, solid state electrochemistry and magnetic properties are
described. Compound 2-(SS) is an antiferromagnet (TN = 4.8 K) with the coexistence
of both redox activity and chirality. It also shows a field-induced magnetic phase
transition.
Scheme 1
Experimental Section
Starting materials
All reagents and solvents were commercially available and were used as received
without further purification. The ligand H2TTFbp and [(n-Bu)4N][Fe(TTFbp)(CN)2]
were prepared according to literature procedures.15 (R,R)- and (S,S)-
[Mn(salphen)(H2O)2]ClO4 were prepared according to the published methods.16 (R,R)-
and (S,S)-H2salphen (Scheme 1), were synthesized from the condensation of
salicylaldehyde with 1,2-diphenylethylenediamine in a molar ratio of 2:1 in ethanol,
respectively.
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Caution! Although no problems were encountered in this work, perchlorate salts are
potentially explosive and cyanides are very toxic. Thus, these starting materials
should be handled in small quantities and with great care.
Preparation of H2TTFbp (L). A solution of picolinic acid (246 mg, 2.00 mmol) in
pyridine (3 mL) was added to a solution of 5,6-diamino-2-(4,5-bis(methylthio)-1,3-
dithio-2-ylidene)-benzo[d]-1,3-dithiole (432 mg, 1.00 mmol) in pyridine (3 mL). To
this reaction mixture, triphenyl phosphite (621 mg, 2.00 mmol) was added dropwise.
After heating of the mixture to 100 °C for 8 h and cooling to room temperature, a
yellow precipitate was isolated by filtration and washed with cold ethanol. Yield: 427
mg (73%). Anal. Calcd for C24H18N4O2S6: C, 49.12; H, 3.09; N, 9.55. Found: C,
1
49.24; H, 3.01; N, 9.33. H NMR (500 MHz, CD2Cl2, 298 K) δ (ppm) = 2.44 (s, 6H,
CH3), 7.53-7.47 (m, 2H, ArH), 7.89 (s, 2H, ArH), 7.93 (td, 2H, J = 7.7, 1.5 Hz, ArH),
8.26 (d, 2H, J = 7.8 Hz, ArH), 8.55 (d, 2H, J = 4.6 Hz, ArH), 10.17 (s, 2H, NH). m/z
(MALDI-TOF): 586.236.
Preparation of [(n-Bu)4N][Fe(TTFbp)(CN)2] (1). To a solution of H2TTFbp (586
mg, 1.00 mmol) and NaOH (80 mg, 2.00 mmol) in 100 mL of methanol, a solution of
FeCl3·6H2O (270 mg, 1.00 mmol) in 10 mL of methanol was added. After 3 h of
refluxing, a solution of [(n-Bu)4N][CN] (540 mg, 2.00 mmol) in methanol was added.
The resulting mixture was heated to reflux for 24 h and then filtered to remove the
insoluble solid. The filtrate was concentrated under vacuum to a small volume. After
cooling down, black microcrystals of [(n-Bu)4N][Fe(TTFbp)(CN)2] precipitated.
Single crystals suitable for X-ray crystallography were obtained by slow
recrystallization of this material from a CH3OH solution. Yield: 452 mg (48%). Anal.
Calcd for C42H52FeN7O2S6: C, 53.95; H, 5.61; N, 10.49. Found: C, 53.88; H, 5.34; N,
10.65. Selected IR data (KBr, cm−1): 2123 (v(C≡N)). m/z (ESI): 692.00 (M−)
Preparation of [Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n (2-(RR)). A solution of
[Mn((R,R)-salphen)(H2O)2]ClO4 (24.8 mg, 0.04 mmol) in 4 mL of acetonitrile was
added to a solution of [(n-Bu)4N][Fe(TTFbp)(CN)2] (37.40 mg, 0.04 mmol) in 20 mL
of methanol. After 30 min of stirring, the resulting solution was filtered and then left
undisturbed. The slow evaporation of the filtrate at room temperature yielded black
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needle crystals of 2-(RR) after two weeks. Yield: 43%. Anal. Calcd for C54H38FeMn
N8O4S6: C, 55.62; H, 3.28; N, 9.61. Found: C, 55.52; H, 3.43; N, 9.46. Selected IR
data (KBr, cm−1): 2126 (v(C≡N)).
Preparation of [Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n (2-(SS)). The preparation
was similar to that of 2-(RR) with the exception that [Mn((S,S)-salphen)(H2O)2]ClO4
was used. After 30 min of stirring, the resulting solution was filtered and then left
undisturbed. The slow evaporation of the filtrate at room temperature gave black
needle crystals of 2-(SS) after two weeks. Yield: 43%. Anal. Calcd for C54H38FeMn
N8O4S6: C, 55.62; H, 3.28; N, 9.61. Found: C, 55.54; H, 3.41; N, 9.47. Selected IR
data (KBr, cm−1): 2126 (v(C≡N)).
X-ray Structure Determination. The crystal structures were determined with a
Siemens (Bruker) SMART CCD diffractometer using monochromated Mo K
radiation ( = 0.71073 Å). The cell parameters were retrieved using SMART software
and refined using SAINT17 for all observed reflections. Data was collected using a
narrow-frame method with scan widths of 0.30° in  and an exposure time of 10
s/frame. The absorption corrections were applied using SADABS18 supplied by
Bruker. Structures were solved by direct methods using the program SHELXL-97.19
The positions of metal atoms and their first coordination spheres were located from
direct methods E-maps. The other non-hydrogen atoms were found in alternating
difference Fourier syntheses and least-squares refinement cycles and, during the final
cycles, refined anisotropically. Hydrogen atoms were placed in calculated positions
and refined as riding atoms with a uniform value of Uiso. Final crystallographic data
and values of R1 and wR2 are listed in Table 1. Selected bond distances and angles for
complexes 1, 2-(RR) and 2-(SS) are listed in Tables 2-3 and Table S1, respectively.
CCDC reference numbers are 1454969 (1), 1454970 (2-(RR)), 1454971 (2-(SS)).
Physical Measurements. Elemental analyses for C, H and N were performed on a
1
Perkin-Elmer 240C analyzer. H NMR spectra were measured on a Bruker AM 500
II
spectrometer. Mass spectra were recorded on a Bruker Autoflex TM instrument for
MALDI-TOF-MS or on a Varian MAT 311A instrument for ESI-MS. CD spectra
were recorded on a Jasco J-810 spectropolarimeter. IR and VCD spectra in the region
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of 1800–800 cm−1 were recorded on a VERTEX 80v Fourier transform infrared
spectrometer equipped with a PMA 50 VCD/IRRAS module (Bruker, Germany) using
previous procedures.20 The solid samples were prepared by mixing the compound and
KBr in a 1:200 ratio, and pressing the pellet in a Perkin Elmer hydraulic pellet press
for 5 min under 10 tons of pressure. The photo elastic modulator (PEM) was set to
1500 cm-1, and the spectral resolution was 4 cm−1. All VCD measurements were
collected for 1 h composed of 4 blocks in 15 min. Baseline correction was performed
with the spectrum of a pure KBr pellet using the same measurement setup. Magnetic
susceptibilities for polycrystalline samples were measured with the use of a Quantum
Design MPMS-SQUID-VSM magnetometer in the temperature range 1.9–300 K.
Field dependences of magnetization were measured in an applied field up to 70 kOe.
Solid state cyclic voltammetry (CV) was performed using a BASi Epsilon
Electrochemical Analyzer with ferrocene (Fc) as an internal reference. Measurements
were conducted under an inert Ar atmosphere using a conventional 3-electrode cell
with a glassy carbon working electrode containing the immobilized solid, a Pt wire
auxiliary electrode and an Ag/Ag+ quasi reference electrode. A 0.1 M
tetrabutylammonium
hexafluorophosphate
([(n-Bu)4N]PF6/CH3CN
or
[(n-Bu)4N]PF6/DMF) supporting electrolyte was employed.
Results and discussion
Synthesis and Characterization
The versatile dicyanideferrite building block [(n-Bu)4N][Fe(TTFbp)(CN)2] with a
planar π- conjugated TTF annulated ligand was successfully synthesized from the
H2TTFbp ligand, FeCl3·6H2O and [(n-Bu)4N][CN] in methanol. The use of equimolar
amounts of [(n-Bu)4N][Fe(TTFbp)(CN)2] and the enantiopure precursors
[Mn((R,R)-salphen)(H2O)2][ClO4] or [Mn((S,S)-salphen)(H2O)2][ClO4], afforded two
chiral one-dimensional complexes. The characterization of these complexes has been
accomplished by CD and VCD spectra, cyclic voltammetry, X-ray diffraction analysis
and magnetic susceptibility measurements.
Spectroscopic Studies
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The optical activity and enantiomeric nature of 2-(RR) and 2-(SS) were confiDrmOI:e1d0.1b03y9/C6DT01756H
circular dichroism (CD) spectroscopy measurements in KBr pellets (Fig. 1). The
solid-state CD spectrum of 2-(RR) (R isomer) exhibits a negative Cotton effect at max
= 247 and 318 nm, while 2-(SS) (S isomer) shows Cotton effects of the opposite sign
at the same wavelengths. The CD signals for the two compounds are a clear mirror
image.
Vibrational circular dichroism (VCD) is a powerful technique in the study of chiral
molecules. It is the extension of CD into the infrared region of a spectrum which
reflects vibrational transitions, and has aided in reaching a deeper understanding of
the configuration of chiral molecules.8b,20 As expected, no noticeable difference in the
signals of the enantiomers were detected from the IR, while the VCD spectra appear
as approximately mirror image forms (Fig. 2). In the IR spectra, the absorption
features arise from the imine double bonds stretch vibrations (1625, 1601 cm1 for
2-(RR) and 2-(SS) and C−H deformations (1444, 1306 and 1294 cm1 for 2-(RR) and
2-(SS)). In the corresponding VCD spectra, the two imine chromophores manifest as a
couplet curve, while the latter appear as incisive peaks.
Fig. 1 CD spectra of 2-(RR) and 2-(SS) in KBr pellets
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Fig. 2 VCD (top) and IR absorption (bottom) spectra of 2-(RR) and 2-(SS)
Structural Description
The crystal structure of the precursor (complex 1) is shown in Fig. 3. It consists of
one mononuclear [Fe(TTFbp)(CN)2] unit and one [(n-Bu)4N]+ cation. In each
[Fe(TTFbp)(CN)2] anion, the central iron(III) ion is coordinated by two carbon atoms
from cyanide units, two amide-nitrogen atoms and two pyridine nitrogen atoms from
the TTFbp moieties, giving a distorted octahedral coordination structure. The Fe−N
(1.894(3)−2.002(3) Å) and Fe−C (1.974(5)−1.982(5) Å) bond lengths are in good
agreement with those observed previously in related compounds.15 The Fe−C≡N
angles for the cyanide groups (178.9(4) and 178.8(4)°) depart slightly from linearity.
The central C=C bond of the TTF core is 1.335(6) Å in length, confirming the neutral
form of the TTF moiety.11a
Table 1. Summary of crystallographic data for all complexes
1
2-(RR)
2-(SS)
formula
Fw
C42H52FeN7O2S6
935.12
C54H38FeMnN8O4S6
1166.07
C54H38FeMnN8O4S6
1166.07
crystal system
space group
a, Å
Triclinic
P-1
Triclinic
Triclinic
P1
P1
10.823(2)
20.388(4)
24.414(5)
10.5144(13)
12.1188(15)
22.247(3)
10.5901(15)
13.2993(19)
21.701(3)
b, Å
c, Å
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α, deg
β, deg
γ, deg
V, Å3
Z
83.518(4)
82.033(4)
78.424(4)
5206(2)
4
96.993(2)
94.9850(10)
96.292(2)
2782.3(6)
2
97.500(3)
93.232(2)
94.499(3)
3014.0(7)
2
calcd, g cm3
1.193
1.392
1.285

T / K
296(2)
293(2)
296(2)
, mm1
, deg
F(000)
0.569
0.764
0.706
0.85 to 27.39
1964
0.93 to 25.50
1194
1.32 to 25.00
1194
−13  h  13
−24  k  26
−31  l  30
−12  h  8
−14  k  14
−26  l  26
−12  h  12
−15  k  14
−25  l  25
index ranges
data/restraints
/parameters
GOF (F2)
23223 / 29 / 1009
14965 / 3 / 1338
13352 / 3 / 1333
0.953
1.044
1.499
a
b
0.0674, 0.1755
0.0901, 0.2306
0.1338, 0.3477
R1 ,wR2 (I>2(I))
a
b
R1 , wR2 (all data)
0.1464, 0.1968
0.1174, 0.2539
0.1579, 0.3758
a
b
2
2 2 1/2
R1 = ||Fo|  |Fc||/Fo|. wR2 = [w(Fo  Fc2)2/w(Fo ) ]
Table 2 Selected bond lengths (Å) and angles (°) for complex 1.
Bond Distances (Å)
Fe(1)-N(5)
Fe(1)-N(7)
Fe(1)-C(51)
C(31)-C(32)
1.894(3)
2.003(3)
1.982(5)
1.335(6)
Fe(1)-N(6)
Fe(1)-N(8)
Fe(1)-C(52)
1.901(3)
2.000(3)
1.974(5)
Bond Angles (°)
N(12)-C(52)-Fe(1)
N(11)-C(51)-Fe(1)
178.9(4)
178.8(4)
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Fig. 3 View of the [Fe(TTFbp)(CN)2] unit. The [(n-Bu)4N]+ cation and hydrogen
atoms are omitted for clarity.
2-(RR) and 2-(SS) are a pair of enantiomers and crystallize in the chiral space group
P1 (Fig. 4 and Fig. S1). They are composed of a [Fe(TTFbp)(CN)2] anion and a
[Mn(salphen)]+ cation, forming neutral cyano-bridged linear-like double chains with
the repeating units (−MnIII−NC−FeIII−CN−)n. As shown in Fig. 5, complex 2-(SS) has
two types of [Fe(TTFbp)(CN)2] (including Fe1 and Fe2 atoms, respectively). Both
FeIII centers of the compounds are coordinated by four nitrogen atoms from the
TTFbp2 ligand located at its equatorial plane and two trans cyanide carbon atoms,
yielding a distorted octahedral coordination geometry. The Fe−C (1.92(2)−1.964(18)
Å) and Fe−N (1.835(16)−2.021(16) Å) bond lengths are in good agreement with those
observed previously in related compounds.21 The Fe−C≡N angles for the bridging
cyanide groups (169.9(18)−178.5(19)°) depart slightly from linearity. There are also
two crystallographically independent MnIII ions in 2-(SS), Mn1 and Mn2. The MnIII
ions adopt the same coordination mode, which consists of two axially-ligated cyanide
groups (2.245(17) and 2.310(15) Å for Mn1, 2.336(17) and 2.267(16) Å for Mn2),
two imino-nitrogen atoms and two phenolic oxygen atoms from the salphen ligand
(1.964(15) and 1.970(17) Å for Mn1−N, 1.928(13) and 1.860(13) Å for Mn1−O,
1.964(16) and 2.029(16) Å for Mn2−N, and 1.855(13) and 1.880(12) Å for Mn2−O).
The axial elongation results from the well-known Jahn-Teller effect on an octahedral
high-spin MnIII ion.22 The Mn−N≡C angles range from 153.1(17) to 165.1(18),
deviating significantly from linearity. The chains extend along the a axis with an
intrachain Fe–Mn separation of 5.284−5.286 Å through bridging cyanide. The
shortest interchain Fe∙∙∙Fe, Mn∙∙∙Mn, and Fe∙∙∙Mn distances are 8.615, 7.846 and 8.464
Å, respectively−longer than the intrachain metal-metal distance. Each chain interacts
with two other adjacent chains by nonclassical hydrogen bonds C(58)–H(58)···O(3)
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(H···O distance, 2.44 Å) and C(31)–H(31)···S(12) (H···S distance, 2.85 Å), thuVsiew Article Online
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forming a two-dimensional (2D) layer (ESI, Fig. S2). The layers stack to form a
three-dimensional (3D) structure along the b axis via weak H-bonding interactions
(ESI, Fig. S3).
Fig. 4 Perspective view of the infinite one-dimensional zigzag chains of 2-(RR) (a)
and 2-(SS) (b). Hydrogen atoms are omitted for clarity.
Fig. 5 Perspective drawing of the crystallographic structural unit of 2-(SS) showing
the atom numbering. Hydrogen atoms are omitted for clarity.
Table 3. Selected bond lengths (Å) and angles (°) for complex 2-(SS)
Bond Distances (Å)
Fe(1)-N(1)
Fe(1)-N(3)
Fe(1)-C(53)
Fe(2)-N(9)
1.895(15)
1.980(18)
1.964(18)
1.914(17)
Fe(1)-N(2)
Fe(1)-N(4)
Fe(1)-C(54)
Fe(2)-N(10)
1.862(18)
2.021(16)
1.928(19)
1.835(16)
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Fe(2)-N(11)
Fe(2)-C(107)
C(19)-C(20)
Mn(1)-O(3)
Mn(1)-N(5)
Mn(1)-N(7)
Mn(2)-O(7)
Mn(2)-N(13)
Mn(2)-N(15)
1.966(17)
Fe(2)-N(12)
Fe(2)-C(108)
C(73)-C(74)
Mn(1)-O(4)
Mn(1)-N(6)
Mn(1)-N(8)
Mn(2)-O(8)
Mn(2)-N(14)
Mn(2)-N(16)
2.016(19)
1.96(2)
1.92(2)
1.36(3)
1.37(3)
1.928(13)
1.964(15)
2.245(17)
1.880(12)
1.964(16)
2.336(17)
1.860(13)
1.970(17)
2.310(15)
1.855(13)
2.029(16)
2.267(16)
Bond Angles (°)
N(7)-C(53)-Fe(1)
N(15)-C(107)-Fe(2)
N(1)-Fe(1)-C(53)
N(1)-Fe(1)-C(54)
C(54)-Fe(1)-C(53)
C(54)-Fe(1)-N(4)
C(54)-Fe(1)-N(3)
N(9)-Fe(2)-C(108)
N(9)-Fe(2)-C(107)
C(53)-N(7)-Mn(1)
C(107)-N(15)-Mn(2)
O(4)-Mn(1)-N(8)
N(5)-Mn(1)-N(8)
O(4)-Mn(1)-N(7)
N(5)-Mn(1)-N(7)
N(8)-Mn(1)-N(7)
O(7)-Mn(2)-N(16)
N(13)-Mn(2)-N(16)
O(7)-Mn(2)-N(15)
N(13)-Mn(2)-N(15)
176(2)
N(8)#2-C(54)-Fe(1)
N(16)#1-C(108)-Fe(2)
N(2)-Fe(1)-C(53)
N(2)-Fe(1)-C(54)
C(53)-Fe(1)-N(4)
C(53)-Fe(1)-N(3)
N(10)-Fe(2)-C(108)
N(10)-Fe(2)-C(107)
C(108)-Fe(2)-C(107)
C(54)#1-N(8)-Mn(1)
C(108)#2-N(16)-Mn(2)
O(3)-Mn(1)-N(8)
178.5(19)
177(2)
169.9(18)
95.4(7)
93.0(7)
170.0(8)
89.0(7)
88.0(8)
91.1(8)
95.5(8)
165.1(18)
157.1(18)
93.2(6)
86.8(6)
93.5(6)
85.9(6)
171.7(5)
91.2(6)
89.1(6)
93.8(6)
87.6(7)
91.6(8)
94.6(8)
84.2(7)
88.1(8)
89.7(7)
96.0(7)
171.7(8)
163.0(17)
153.1(17)
90.0(6)
86.8(6)
94.4(6)
88.3(7)
90.0(6)
87.6(6)
92.9(6)
87.1(6)
174.0(5)
N(6)-Mn(1)-N(8)
O(3)-Mn(1)-N(7)
N(6)-Mn(1)-N(7)
O(8)-Mn(2)-N(16)
N(14)-Mn(2)-N(16)
O(8)-Mn(2)-N(15)
N(14)-Mn(2)-N(15)
N(16)-Mn(2)-N(15)
Symmetry transformations used to generate equivalent atoms are given in footnotes #1 to #2.
#1x-1, y, z. #2x+1, y, z.
Electrochemical Properties.
The cyclic voltammogram (CV) of H2TTFbp (Fig. 6a) displays two distinct,
reversible oxidation waves at E1/2 = 0.15 and 0.31 V which are assigned to the
TTF/TTF•+ and TTF•+/TTF2+ redox couples, respectively. The cathodic region reveals
one irreversible reduction process at 2.26 V which can assigned to the reduction of
the amide functionality. Furthermore, two very close, quasi-reversible reduction
processes at E1/2 = 2.43 and 2.54 V are tentatively assigned to the reductions of the
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two pyridyl rings. CVs collected over a range of scan rates (Fig. 6b) indicate that the
electrochemical processes occur independent of the scan rate.
(b)
(a)
Fig. 6 Solution state CV of H2TTFbp (a) over 3 full cycles at 100 mV/s and, (b) single
scans over multiple scan rates. Measurements were performed in 0.1 M
[(n-Bu)4N]PF6/DMF electrolyte and were referenced to Fc/Fc+. Arrows indicate the
direction of the forward scan.
Solution state cyclic voltammetry of [(n-Bu)4N][Fe(TTFbp)(CN)2]reveals two
reversible oxidation waves at E1/2 = 0.06 and 0.41 V which were assigned to the
TTF/TTF•+ and TTF•+/TTF2+ couples, respectively (Fig. 7a). The spike at 0.72 V
observed at scan rates over the range 10-400 mV/s is tentatively assigned to chemical
interaction between the compound and the glassy carbon working electrode,as this
feature was not observed at a faster scan rate of 800 mV/s. A reversible oxidation
wave was observed at E1/2 = 0.78 V which may be due to oxidation of FeIII to FeIV. At
E1/2 = 1.16 V, a reversible reduction wave due to the FeIII/II redox couple was
observed. Cycling of the redox potential between 1.5 and 2.5 V revealed
reproducible CVs, demonstrating the reversibility and stability of the compound in its
various redox states. Over multiple scan rates, the positions of the aforementioned
redox processes did not shift in potential, indicating the scan rate independence of
[(n-Bu)4N][Fe(TTFbp)(CN)2] (Fig. 7b). The absence of any distinct reduction
processes reinforces the assignment of the reductions in H2TTFbp to a chemical
change to the amide and pyridyl moieties which become less accessible once
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coordinated to the FeIII center.
(a)
(b)
Fig. 7 Solution state CV of [(n-Bu)4N][Fe(TTFbp)(CN)2] showing (a) 3 subsequent
cycles at 100 mV/s and (b) single scans over multiple scan rates. The asterisk marks a
current spike due to solute-electrode interactions. Measurements were performed in
0.1 M [(n-Bu)4N]PF6/CH3CN electrolyte and were referenced to Fc/Fc+. Arrows
indicate the direction of the forward scan.
Coordination of [(n-Bu)4N][Fe(TTFbp)(CN)2] to a [Mn(salphen)]+ cation results in
the appearance of new features in the oxidative region of the CV for 2-(SS). The solid
state CV of 2-(SS) reveals quasi-reversible oxidation processes which result in the
decomposition or dissolution of the complex in the electrolyte, 0.1 M
[(n-Bu)4N]PF6/CH3CN. Scan rate dependence studies reveal three irreversible
reduction processes at onset potentials of 0.37, 0.89 and 1.10 V which are most
prominent at scan rates of 20, 50, 200, 400 and 800 mV/s. These processes are likely
to be attributable to the TTF/TTF•+, TTF•+/TTF2+ and MnIII/IV redox couples,
respectively (ESI, Table S2). At 100 mV/s however, a fourth irreversible oxidation
peak was observed at an onset potential of 0.57 V (Fig. 8a). On first inspection, the
cathodic region appears to be featureless, however, upon closer examination, a
quasi-reversible reduction wave is observed at E1/2 = 0.66 V, and is attributed to the
FeIII/II couple. The shift in this couple to a less cathodic potential upon coordination to
[Mn(salphen)]+ is consistent with electron density being redistributed across the
shared cyanide ligand. Two further successive cycles were featureless owing to the
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irreversible nature of these redox processes.
(a)
(b)
Fig. 8 Solid state CV of 2-(SS) (a) over 3 subsequent cycles at 100 mV/s and (b)
single scans over multiple scan rates. Measurements were performed in 0.1 M
TBAPF6/CH3CN electrolyte and were referenced to Fc/Fc+. Arrows indicate the
direction of the forward scan.
Magnetic Properties
The dc magnetic susceptibility data for complex 2-(SS) were collected at 1000 Oe in
the 2-300 K range, as shown in Fig. 9. The χMT value at room temperature is 3.34
cm3·K·mol1 per FeIIIMnIII unit, which is close to the theoretical value (3.38
cm3·K·mol1) calculated for a noncoupled FeIII center (S = 1/2) and MnIII center (S = 2)
assuming g = 2.00. As the temperature is lowered, the χMT value is almost constant
above 50 K, and then decreases to 0.61 cm3·K·mol1 at 2 K, demonstrating the weak
antiferromagnetic coupling between cyanide-bridged FeIII-MnIII. The magnetic
susceptibility above 30 K obeys the Curie-Weiss law, with a Curie constant of 3.36
cm3·K·mol1 and a Weiss constant of −1.67 K (ESI, Fig. S4). The negative  confirms
the presence of antiferromagnetic interactions among magnetic centers.
To estimate the magnetic coupling of the single chain complexes, we applied an
analytical expression derived from an alternating ferrrimagnetic chain model (H =
‒JΣiSFei[(1+α)SMni+(1-α)SMni+1]).23 The best fit over the temperature range 50-300 K
gives gMn = 1.99, gFe = 2.01, J = −0.96 cm1, α = 0.34 and zJ’ = −0.34 (R = 3.21 
105). The negative value of J indicates antiferromagnetic couplings between FeIII and
MnIII ions within the chain.
The field dependence of magnetization was measured up to 70 kOe at 1.9 K (Fig.
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10). The inconspicuous S-shaped curve increases to a maximum value of 3.40 Nβ at
70 kOe which is slightly higher the expected value of 3 Nβ calculated from g = 2.00.
Importantly, the magnetization will continuously increase with the field, and it is
suggested that decoupling occurs at high field. This result also confirms that the
antiferromagnetic coupling between spin centers is very weak. From the dM/dH vs H
plot at 1.9 K (inset of Fig. 10), the critical field is estimated to be about 35 kOe.
Below 35 kOe, 2-(SS) has an antiferromagnetic spin ground state; above this field, the
decoupling effect of the field leads to the paramagnetic phase in this complex. To
further elucidate the magnetic behavior, we recorded χM vs T data for 2-(SS) under
several fields as shown in the inset of Fig. 9. A maximum of χM was observed at about
4.8 K under 10 kOe. The peak broadens and shifts to lower temperature as the
magnetic field increases, and it finally disappears for H  40 kOe. This behavior
shows the existence of a field-induced magnetic phase transition.
The alternating current (ac) susceptibility of complex 2-(SS) was measured over the
frequency range 1−999 Hz at 2−16.0 K under zero dc field (Fig. 11). The in-phase
(χM') susceptibility has a maximum around 4.8 K, with no peaks observed in the
out-of-phase susceptibility (χM'') at the same temperature, suggesting an absence of
single-chain magnetism below this temperature.
Fig. 9 Temperature dependence of the χMT product for 2-(SS) at 1 kOe. The red solid
line represents the best fits of the data. (Inset) Thermal dependence of the magnetic
susceptibility at T19 K.
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Fig. 10 Field dependence of magnetization at 1.9 K for 2-(SS). (Inset) dM/dH vs H
plot.
Fig. 11 Temperature dependence of the in-phase χM' (top) and out-of-phase χM''
(bottom) at different frequencies with a zero applied dc field for 2-(SS).
Magneto-structural correlation
In cyanide-bridged FeIII and MnIII systems, the magnetic coupling between low-spin
5
0
3
1
FeIII (t2g eg ) and high-spin MnIII(t2g eg ) through cyanide is either ferro- or
antiferromagnetic. Regarding the nature of the FeIII and MnIII interaction, the
orthogonality of the magnetic orbitals dπ in FeIII and dz2 in MnIII will lead to
ferromagnetic interactions, while the orbital overlap between dπ orbitals of FeIII and
MnIII gives rise to antiferromagnetic interactions. The overall magnetic properties
depend on which contribution predominates. As shown in Table 4, structural and
magnetic parameters of some 1D cyanide-bridged FeIII-MnIII complexes based on
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[FeL(CN)2] are summarrized for comparasion.21c,24 It is noted that ferromagnetic
properties are common in cyanide-bridged FeIII-MnIII complexes, suggesting that the
orbital orthogonality effect usually overwhelms the orbital overlap effect. Considering
the stronger delocalization (σ-type) of the spin density from the MnIII occurring on the
cyanide group, the dz2 orbital of MnIII is the major contributor to the magnetic
coupling. Thus, ferromagnetic properties are more usual. By analyzing the
relationship between Mn-N≡C bond angles and the magnetism, we concluded that the
magnetic coupling of FeIII-MnIII changes from ferromagnetic to antiferromagnetic
with an increasing Mn-N≡C angle. This feature indicates that the increase of the
Mn-N≡C angles plays a crucial role in improving the overlap of magnetic Fe and Mn
dπ orbitals, resulting in the dominance of JAF over JF, and in turn favoring
antiferromagnetic couplings. Similar magnetic features were also found in other
cyanide-bridged FeIII-MnIII systems.21c,25 It should be noted that, the Mn-N≡C bond
angle in this system is larger than some cyano-bridged Fe(III)-Mn(III) complexes in
Table 4. We assume that the steric effect originates from TTF moieties and leads to
the larger Mn-N≡C bond angle, since the volume of the TTFs is significantly larger
than other simple ligands used in similar cyano-briged Fe(III)-Mn(III) complexes.
DOI: 10.1039/C6DT01756H
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Table 4 Structural and Magnetic Parameters for some cyano-bridged FeIII-MnIII Complexes
Compound
Structure
1D
Mn-Ncyano(Å)
C≡N-Mn(°)
magnetism
ref
24a
[Mn(5-Cl-salen)Fe(bpClb)(CN)2]n
[Mn(5-Cl-salen)Fe(bpb)(CN)2]n
[Mn(5-Br-salen)Fe(bpb)(CN)2]n
[Mn(5-Me-salen)Fe(bpb)(CN)2]n
[Mn(saltmen)Fe(bpb)(CN)2]n
[Mn(salen)][Fe(bpb)(CN)2]n
2-(SS)
2.258(4)–2.277(4)
2.270(7)–2.339(7)
2.304(3)–2.372(3)
2.308(3)–2.376(3)
2.242(6)–2.328(5)
2.301(3)–2.439(3)
2.245(17)–2.336(17)
149.5(4), 154.3(3)
149.1(7)–160.8(7)
149.0(3)–161.3(2)
147.5(2)–160.9(3)
148.8(5)–166.0(6)
151.8(3), 158.6(3)
153.1(17)–165.1(18)
F
F
1D
24a
1D
F
24a
1D
F
24a
1D
F
24b
1D
AF
AF
24c
1D
This work
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Conclusion
In summary, we have introduced a redox-active TTF ligand into the dicyanideferrite
building block [(n-Bu)4N][Fe(TTFbp)(CN)2] for the first time. Two enantiopure
one-dimensional complexes, [Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n (2-(RR)) and
[Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n (2-(SS)), were subsequently synthesized and
structurally characterized. Circular dichroism and vibrational circular dichroism
spectra confirm the enantiomeric nature of the optically active complexes, while
solution and solid state CV studies reveal that complexes exhibit multiple
redox-accessible states. Magnetic studies show that antiferromagnetic coupling is
operative between FeIII and MnIII centers bridged by cyanide. The intermolecular
hydrogen interactions of compound 2-(SS) lead to an antiferromagnet with TN = 4.8 K.
A field-induced magnetic phase transition was also observed in 2-(SS), and was
ascribed to the decoupling effect of the field. Magnetostructural correlations for some
typical cyano-bridged heterobimetallic FeIII−MnIII compounds were also instructive in
elucidating the origins of the magnetic behavior. The introduction of the redox-active
TTF unit, coupled with chirality into cyanide-bridged complexes with interesting
magnetic properties makes it possible to construct interesting multifunctional
materials. Further investigations into the partial oxidation of these compounds via
chemical and electrochemical methods will pave the way towards applications of
these new materials, and this work is currently underway in our laboratory.
Supporting Information
Additional structures, electrochemical data and magnetic characterization data, and
X-ray crystallographic files in CIF format for 1, 2-(RR) and 2-(SS). This material is
available free of charge via the Internet at http://www.rsc.org.
Acknowledgments
This work was supported by the Major State Basic Research Development Program
(2013CB922101), the National Natural Science Foundation of China (91433113), and
the Australian Research Council (DP110101671). We also thank Dr. Tian-Wei
Wang for experimental assistance on magnetic measurements.
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Page 25 of 25
Dalton Transactions
View Article Online
DOI: 10.1039/C6DT01756H
Graphical Abstract
Two enantiopure one-dimensional complexes were synthesized by the reaction
between chiral MnIII Schiff-base complexes and the redox-active dicyanideferrite
building block [(n-Bu)4N][Fe(TTFbp)(CN)2]. Circular dichroism (CD) and vibrational
circular dichroism (VCD) spectra confirm the enantiomeric nature of the optically
active complexes. Solid state CV studies reveal the redox-active properties of the
complexes. Antiferromagnetic couplings between FeIII and MnIII centers are present
within a chain and a field-induced magnetic phase transition is observed (TN = 4.8 K)
for compound 2-(SS).