Ligand-directed assembly of trinuclear and one-dimensional heterotrimetallic CuIILnIIIFeIII complexes: Unusual antiferromagnetic CuIIFeIII coupling: Via cyano bridges

Article abstract of DOI:10.1039/c6nj01887d

New heterotrimetallic complexes [Cu(valpn)(H₂O)Ln(H₂O)₃Fe(CN)₆]·xH₂O (Ln = Gd, x = 3 for complex 1; Ln = Tb, x = 3 for complex 2; Ln = Dy, x = 1.75 for complex 3; H₂valpn = N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane), {[Cu(Me₂valpn)]₂Ln(H₂O)Fe(CN)₆·xH₂O·yCH₃CN}_n (Ln = Gd, x = 5, y = 2.5 for complex 4; Ln = Tb, x = 4.5, y = 1.5 for complex 5; Ln = Dy, x = 5.5, y = 2.5 for complex 6; Ln = Y, x = 6, y = 4 for complex 7; H₂Me₂valpn = N,N′-bis(3-methoxysalicylidene)-2,2-dimethyl-1,3-diaminopropane) have been synthesised by a reaction of Cu(valpn) (or Cu(Me₂valpn)), Ln³⁺ and [Fe(CN)₆]^3- in a molar ratio of 2:1:1. Complexes 1-3 have a CuLnFe trinuclear structure, consisting of phenoxo-bridged Cu-Ln and cyano-bridged Ln-Fe moieties. Complexes 4-7 contain phenoxo-bridged Cu₂Ln units that are connected by [Fe(CN)₆]^3- to form a one-dimensional (1D) zig-zag structure. In the trinuclear complexes 1-3, the [Fe(CN)₆]^3- anion coordinates to Ln³⁺, whereas it coordinates to Cu²⁺ in complexes 4-7. Magnetic studies demonstrate that there exists a ferromagnetic interaction between Cu(ii) and Gd(iii) ions via the phenoxo bridges, while the cyano-bridges transit antiferromagnetic coupling between low-spin Fe(iii) and Cu(ii) or Gd(iii). The fitting to the magnetic susceptibilities of complexes 1 and 4 gave the parameters of J_CuGd = 2.392 and 2.945 cm^-1, and J_FeGd = -0.341 cm^-1 and J_FeCu = -0.378 cm^-1. The ac magnetic measurements reveal that complex 6 shows slow magnetization relaxation with an energy barrier of 12.3 K and a relaxation time of τ₀ = 1.65 × 10^-6 s, which is typical of a single-chain magnet.

Full text of DOI:10.1039/c6nj01887d

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New Journal of Chemistry
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DOI: 10.1039/C6NJ01887D
New J. Chem.
ARTICLE
Ligand-directed assembly of trinuclear and one-dimensional
heterotrimetallic CuIILnIIIFeIII complexes. Unusual
antiferromagnetic CuIIFeIII coupling via cyano bridges
Received 00th January 20xx,
Accepted 00th January 20xx
Mei-Jiao Liu,a Kong-Qiu Hu,a Cai-Ming Liu,b Ai-Li Cuia and Hui-Zhong Koua,*
DOI: 10.1039/x0xx00000x
New heterotrimetallic complexes [Cu(vapln)(H2O)Ln(H2O)3Fe(CN)6]·xH2O (Ln = Gd, x = 3 for complex 1; Ln = Tb, x = 3
for complex 2; Ln = Dy, x = 1.75 for complex 3; H2valpn = N,N '-bis(3-methoxysalicylidene)-1,3-diaminopropane),
{[Cu(Me2vapln)]2Ln(H2O)Fe(CN)6·xH2O·yCH3CN}n (Ln = Gd, x = 5, y= 2.5 for complex 4; Ln = Tb, x = 4.5, y = 1.5 for
complex 5; Ln = Dy, x = 5.5, y = 2.5 for complex 6; Ln = Y, x = 6, y = 4 for complex 7; H2Me2vapln = N,N '-bis(3-
methoxysalicylidene)-2,2-dimethyl-1,3-diaminopropane) have been synthesised by the reaction of Cu(valpn) (or
Cu(Me2vapln)), Ln3+ and [Fe(CN)6]3- in a molar ratio of 2:1:1. Complexes 1-3 have a CuLnFe trinuclear structure, consisting
of phenoxo-bridged Cu-Gd and cyano-bridged Gd-Fe moieties. Complexes 4-7 contain the phenoxo-bridged Cu2Ln units
that are connected by [Fe(CN)6]3- to form a one-dimensional (1D) zig-zag structure. In the trinuclear complexes 1-3, the
[Fe(CN)6]3- anion coordinates to Ln3+, whereas to Cu2+ in complexes 4-7. Magnetic studies demonstrate that there exists the
ferromagnetic interaction between Cu(II) and Gd(III) ions via the phenoxo bridges, while the cyano-bridges transit
antiferromagnetic coupling between low-spin Fe(III) and Cu(II) or Gd(III). The fitting to the magnetic susceptibilities of
complexes 1 and 4 gave the parameters of JCuGd = 2.392 and 2.945 cm-1, JFeGd = -0.341 cm-1 and JFeCu = -0.378 cm-1. The
ac magnetic measurements reveal that complex 6 shows slow magnetization relaxation with energy barrier of 12.3 K and the
relaxation time 0 = 1.65×10-6 s, typical of a single-chain magnet.
www.rsc.org/
(SB2- = Schiff base ligands) are the main Schiff base metallic
complexes available to obtain trimetallic complexes.7-9 By using
different Schiff base metallic complexes, obtained trimetallic
Introduction
Since the single-molecule magnets (SMMs) and single-chain
magnets (SCMs) were reported, the researches of SMMs and SCMs
have been attracted a wide attention for their potential applications in
information storage.1,2 In the early years, the most reported SMMs
just contained one kind of metallic ions of 3d.3 Considering the large
magnetic momentum and high magnetic anisotropy of 4f metallic
ions, 4f metals were used for synthesizing SMMs.4 For improving
the ground spin values and magnetic anisotropy of complexes, the d
and f metallic ions were combined together and some of these
complexes behaved as SMMs.4d-g Therefore, d-f heherobimetallic
complexes became good candidates for SMMs or SCMs.5 With the
study of magnetic interactions between metallic ions, cyano-,
oxamidato- and phenoxo-bridged trimetallic complexes have been
reported.6 Because heterotrimetallic complexes probably show
improved magnetic properties, the study on trimetallic complexes is
significant.7-11 According to the previous reports, trimetallic SMMs
or SCMs mainly include cyano- and phenoxo-bridged 3d-4f-3d’, 3d-
4f-4d and 3d-4f-5d complexes,7,8 and Ni(SB), Zn(SB) and Cu(SB)
complexes show diverse crystal structures. Under a similar reaction
condition, complex [Cu(valpn)LnFe(CN)6] shows a one-dimensional
structure, while the Ni(II) analog [Ni(valpn)LnFe(CN)6] has a two-
dimensional (2D) layered structure.9b Similarly, complex
[Ni(valpn)Ln(NO3)(H2O)WIV(bpy)(CN)6] has
Interestingly, octanuclear cyclic hetero-trimetallic complexes
[(LnNi2){Fe(CN)6}]2, [(LnZn2){Fe(CN)6}]2 and
[(LnNi2){W(CN)8}]2 based on the Schiff ligand Me2valpn2- have
been reported very recently.8b,9a,11 Although
number of
a
2D structure.10
a
heterotrimetallic complexes based on Cu(SB) reported7a,8a,12 possess
1D chain, trinuclear structure and decanuclear square molecular
structures,8c,12,13,14
[(LnCu2){Fe(CN)6}]2 complexes have been found.
no
similar
cyclic
octanuclear
Considering the Jahn-Teller effect of Cu(II) ion, we expect to
synthesize trimetallic complexes based on Cu(II), Ln(III) and
[Fe(CN)6]3-. We choose bimetallic complexes {[Cu(valpn)]2Ln}3+
and {[Cu(Me2valpn)]2Ln}3+ (Ln3+ = Gd, Tb, Dy) as precursors to
react with K3[Fe(CN)6], respectively. Three trinuclear complexes
[Cu(vapln)(H2O)Ln(H2O)3Fe(CN)6]·xH2O (L = Gd, x = 3 for
complex 1; Ln = Tb, x = 2 for complex 2; Ln = Dy, x = 1.75 for
a.Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China. E-mail:
kouhz@mail.tsinghua.edu.cn; Tel: +86 10 6277 1748
complex
3)
and
four
1D
chain
complexes
b
Beijing National Laboratory for Molecular Sciences, Center for Molecular Science,
{[Cu(Me2vapln)]2Ln(H2O)Fe(CN)6·xH2O·yCH3CN}n (Ln = Gd, x =
5, y= 2.5 for complex 4; Ln = Tb, x = 4.5, y = 1.5 for complex 5; Ln
= Dy, x = 5.5, y = 2.5 for complex 6; Ln = Y, x = 6, y = 4 for
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
†
Electronic Supplementary Information (ESI) available: Additional figures, crystal
date and magnetic data. CCDC 1485723-1485728, 1498898 For ESI and
crystallographic date in CIF or other electric format see DOI: 10.1039/x0xx00000x
.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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ARTICLE
Journal Name
complex 7) have been synthesized. Here, we present the synthesis, the apical position of square pyramidal of Cu1. ThVuiesw, CArutic1lehOanslinae
DOI: 10.1039/C6NJ01887D
structures and magnetic properties of these complexes.
distorted square pyramidal coordination geometry. However,
the O1W-Cu1-Gd1 angle of 72.4(7)° suggests that O1W is
situated at the comparatively proper axial position, and in this
case the Cu1 coordination sphere is close to regular square
pyramidal. Besides O1W and four oxygen atoms from vapln2-,
the other four coordination sites around Gd1 are occupied by
three water oxygen atoms and a cyanide nitrogen atom. The
Gd-O/N bond lengths are in the range of 2.330(3)-2.591(3) Å
for Gd-O, 2.371(3)-2.753(10) Å for Gd-Owater and 2.473(4) Å
for Gd-Ncyano. The GdIII ion exhibits a GdO8N coordination
sphere, and the coordination sphere is close to the Muffin
structure of Cs calculated by the SHAPE software.15 The
Results and discussion
Synthesis and characterizations
Three trinuclear and three 1D Cu(II)-Ln(III)-Fe(III) complexes
have been prepared by the reaction of Cu(II) Schiff bases, the
Ln(III) salts and K3[Fe(CN)6] in the molar ratio of 2:1:1 in a
MeCN-H2O mixture. Unexpectedly, complexes 1-3 of the
valpn2- Schiff base ligand have the metallic molar ratio of 1:1:1
instead of 2:1:1. This phenomenon indicates that the
{[Cu(valpn)]2Ln}3+ precursor is not stable, and decomposes to
form
{[Cu(valpn)]Ln}3+
when
reacting
with
structure of complex
2 is similar to that of complex 1, and the
disorder of O1W and O1W’ similarly exists with the
occupancies of 0.46 and 0.54, respectively (Fig. S1, ESI).
hexacyanoferrite(III). It is worth mentioning that the reaction of
[Cu(valpn)]Gd(NO3)3 with K3[Fe(CN)6] in water gave rise to a
1D double chain complex [Cu(valpn)Gd(H2O)3Fe(CN)6]·4H2O,
Complex
3
has a trinuclear molecular structure (Fig. 1, right),
and . The apparent
where the Gd3+ ion is coordinated by two [Fe(CN)6]3- anions 6b
. The
slightly different from that of complexes
1
2
difference is that the bridging water oxygen atom solely
coordinates to Cu1, and the Dy(III) ion becomes octa-
coordination. Therefore, the O3W-Cu1-Dy1 angle is 87.6°,
normal for apical coordination of O3W towards Cu1. The
coordinate environment of Dy1 is square antiprism (D4d).
formation of trinuclear complexes instead of the 1D double
chain might be due to the presence of excess [Cu(valpn)] that
hamper the coordination of additional [Fe(CN)6]3- to Gd3+.
Previous studies on the Ni(II)-H2Me2valpn-Ln(III)-Fe(III)(CN)6
system have led to the isolation of cyclic octanuclear Ni4Ln2Fe2
complexes.11 However, for the Cu(II)-H2Me2valpn system, 1D
Table 1 Crystal data for complexes 1-3
complexes 4-7 have been obtained. The present result shows
that the metallic ions and the Schiff base ligands can modulate
the molecular structure of the trimetallic complexes.
The IR spectra of complexes 1-3 show strong absorption
peaks at 2095, 2099 and 2090 cm-1, respectively, which are due
to cyanides in Fe[(CN)6]3-. Complexes 4-6 all have two strong
absorption peaks in the cyanide region, 2114, 2146 cm-1 for
complex
1
2
3
C25H34GdFe C25H34TbFe C25H31.5DyFe
Formula
N8CuO11
899.24
N8CuO11
900.91
N8CuO9.75
881.97
293
Monoclinic
P21/c
8.5391(2)
24.9879(8)
15.7226(5)
92.0769(12)
3352.59(17)
4
Formula weight
T (K)
293
293
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P21/c
Monoclinic
P21/c
12.923(3)
12.032(2)
22.590(8)
108.13(3)
3338.1(16)
4
12.889(3)
12.035(2)
22.242(8)
105.12(3)
3330.6(15)
4
complex
complex
4
6
, 2116, 2145 cm-1 for complex
5
, 2114, 2148 cm-1 for
. The splitting of
and 2025, 2110 cm-1 for complex
7
β (º)
V (Å3)
the C≡N stretching vibration suggests the formation of Fe-
C≡N-Cu bridges in complexes 4-7. The strong peaks at 1626-
1635 cm-1 should be assigned to the C=N stretching of the
Z
Dcalcd
1.789
3.091
1.797
1.747
(g·cm-3)
µ (mm-1)
3.230
6148
3.323
6368
1.021
0.0346
0.0883
Schiff base ligands in complexes 1-7
.
Reflections [I >2σ] 6137
Crystal structure
GOF
R1 [I > 2σ(I)]
wR2 (all data)
1.038
0.0352
0.0912
1.035
0.0383
0.1037
Crystal data and structural details for complexes 1–7 are listed
in Table 1 and Table 2, and important bond distances and
angles are collected in Table S1† and Table S2†, respectively.
Table 2 Crystal data for complexes 4-7
Because complexes
complexes and
Complexes 4-7 are isostructural, and crystallize in the
1
and
2 are isomorphous, the structures of
Complex
4
5
6
7
1
3 are described in detail as examples.
C53H67.5GdFe
N12.5Cu2O14
C51H63.5TbFe
N11.5Cu2O13.5
C53H65.5DyFe
N12.5Cu2O12.5
C56H74YFe
N14Cu2O15
Formula
Formula
weight
T (K)
orthorhombic space group, Pbca. The structure for complex
5 is
1443.87
173
1395.48
293
1423.11
293
1455.13
100
described here as a representative.
Crystal
system
Space
group
a (Å)
The crystal structure of complex
1 is shown in Fig. 1 (left).
Orthorhombic
Orthorhombic
Orthorhombic
Orthorhombic
[Fe(CN)6]3- is connected with (CuGd)3+ by a cyanide, affording
a trinuclear structure. The CuII ion is penta-coordinated by the
N2O2 of the Schiff base valpn2- occupying the basal plane, and
the water oxygen atom O1W or O1W’ at the apical position.
O1W and O1W’ are crystallographically disordered, and the
occupancies have been refined to be 0.35 and 0.65, respectively.
Interestingly, O1W’ involves in the weak coordination of Cu1
and Gd1 with the Cu1-O1W’ bond length of 2.714(7) Å and
Gd1-O1W’ bond length of 2.753(10) Å. The O1W’-Cu1-Gd1
angle is 51.8(2)°, indicating that O1W’ severely deviates from
Pbca
Pbca
Pbca
Pbca
21.1918(9)
23.3200(8)
26.6459(12)
13168.2(9)
8
21.134(11)
23.479(12)
26.843(14)
13319(12)
8
21.085(4)
23.379(5)
26.922(5)
13271(5)
8
21.0615(9)
23.2526(9)
26.6468(9)
13049.9(9)
8
b (Å)
c (Å)
V (Å3)
Z
Dcalcd
1.457
1.392
1.424
1.481
(g·cm-3)
µ (mm-1)
GOF
1.914
1.131
1.955
1.022
2.023
1.039
1.815
1.052
R1 [I
2σ(I)]
>
0.0920
0.0683
0.0758
0.0596
2 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
Journal Name
ARTICLE
wR2 (all
data)
View Article Online
DOI: 10.1039/C6NJ01887D
0.2307
0.2171
0.1842
0.1302
The crystal structure of complex
structure of consists of two crystallographically independent
{[Cu(Me2vapln)]2Tb(H2O)}3+ and one [Fe(CN)6]3- anion. The
Cu-Ncyano coordination bonds alternatively link
5 is exhibited in Fig. 2. The
5
{[Cu(Me2vapln)]2Tb(H2O)}3+ with [Fe(CN)6]3-, which leads to
a 1D zig-zag chain. Each [Fe(CN)6]3- is connected with two
{[Cu(Me2vapln)]2Tb(H2O)}3+ fragments through two trans-
cyanides. Both Cu(II) ions are penta-coordinate with a square
pyramidal coordination environment. The coordination sites of
N2O2 from (Me2vapln)2- are situated in the basal plane, and the
apical position is occupied by the nitrogen atom from
[Fe(CN)6]3− with corresponding Cu-Ncyano bond distances of
2.201(7) Å and 2.163(8) Å, respectively. These apical Cu-Ncyano
bond distances are slightly longer than the basal Cu-N/O bond
distances (1.977(6)-1.993(6) Å / 1.962(4)-1.994(5) Å) in the
basal plane. The bridging bond angles of C≡N-Cu are in the
range of 149.2(7)-151.3(7)°. Two crossing Cu(Me2valpn)
moieties chelate the Tb(III) ion with eight oxygen atoms from
the two (Me2vapln)2- ligands, and one oxygen from a water
molecule coordinates to the Tb(III) ion to complete the nine-
coordination sphere. The Tb(III)-O bond lengths are in the
range of 2.338(4)-2.624(5) Å. The coordinate environment of
Tb(III) is near to Muffin or spherical capped square antiprism
calculated by using the SHAPE software.15 The coordination
Fig. 2 Crystal structure of complex
chain structure along the b axis (below). Hydrogen atoms and
solvent molecules have been omitted for clarity.
5
(above) and 1D zig-zag
Magnetic properties
Static magnetic susceptibility. The variable-temperature
magnetic susceptibilities of complexes 1-6 were measured
under an external magnetic field of 1000 Oe. The magnetic date
was collected in the range 2.0-300 K. The measured results are
shown in Fig. 3.
36
32
28
24
20
16
12
8
1 (CuGdFe)
2 (CuTbFe)
3 (CuDyFe)
4 (Cu2GdFe)
5 (Cu2TbFe)
6 (Cu2DyFe)
Fit

modes of {[Cu(Me2vapln)]2Ln(H2O)}3+ in complexes
5 - 7 are
similar to that of cyclic octanuclear complexes
[Ni2(Me2vapln)2Ln(H2O)Fe(CN)6]2.11 The 1D chain structure of
0
50
100
150
T / K
200
250
300
complexes
octanuclare
5
-
7
can be regarded as the open mode of the cyclic
Fig. 3 Temperature dependence of χmT for complexes 1-6. The
solid lines indicate the best fitting results for complexes
[Ni2(Me2vapln)2Ln(H2O)Fe(CN)6]2.11
It is
1
and
4
.
noteworthy that the bridging modes of [Fe(CN)6]3- should be
responsible for the formation of 1D or octanuclear structure,
trans for the former and cis for the latter.
As shown in Fig. 3, the χmT values are 9.19 cm3 K·mol-1
12.81 cm3 K·mol-1 ) and 16.09 cm3 K·mol-1
(
1
),
(
2
(
3
), at room
temperature, close to the theoretical values for a non-coupling
CuLnFe system (Table S3 assuming g = 2.00 for Cu(II) and
low-spin Fe(III)). The slight difference in χmT values should be
due to the presence of Cu(II) and low-spin Fe(III) that usually
have a g factor higher than 2.0, and similar situation occurs to
complexes 4-6 (vide infra). When the temperature decreases,
the χmT value of complex
1 remains constant down to 100 K,
and rapidly increases to a maximum of 10.28 cm3 K mol-1 at 9
K. Then, χmT shows a sharp decrease until 2 K. This behaviour
suggests the presence of
a predominant ferromagnetic
interaction in complex , which is supported by the positive
Curie-Weiss constant (1.465 K). The decrease of χmT below 9
K should be due to the presence of intramolecular Fe-Gd and
1
Fig. 1 Crystal structure of complexes
1 (left) and 3 (right). In
complex , O1W and O1W’ are disordered. Hydrogen atoms
1
and solvent molecules have been omitted for clarity.
intermolecular antiferromagnetic interaction. Complex
a magnetic property similar to that of complex
maximum of χmT at 18 K. For complex , the χmT value
3
shows
1
, with a
2
decreases with the lowered temperature and reaches a minimum
value at 40 K. Below 40 K, χmT increases reaching a maximum
value at 9 K. The high temperature decrease of χmT from 300 K
to 40 K might be due to the thermal depopulation of the excited
Stark sub-levels for Tb(III) that suppress the Cu(II)-Tb(III)
ferromagnetic interaction and the Fe-Tb negligible or weak
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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ARTICLE
ferromagnetic coupling.16 The χmT values of complexes
decrease at lower temperature (9-18 K) upon cooling, which
may be due to the depopulation of Stark sub-levels of Ln(III)
ions and/or the intermolecular antiferromagnetic interaction.
For Gd(III) with the fairly small zero-field splitting of the
ground state (less than 1 cm-1),17 dc magnetic susceptibility of
Journal Name
2
and
3
that contains diamagnetic Y(III). The χmT vs.VieTw AcrtuicrlevOenlionef
complex (Fig. S5
indicates DOtI:h1e0.103p9r/eCs6eNnJc0e1887oDf
7
†)
antiferromagnetic interaction between Cu(II) and Fe(III). The
linear Cu-Fe-Cu trinuclear model with the spin Hamiltonian
ˆ
ˆ
ˆ ˆ
ˆ
operator
has been used for the fitting
H  2JFeCu (SCu1SFe  SFeSCu2
)
to give the fitting parameters of JFeCu = -0.35(1) cm-1, g = 2.24(1)
The JFeCu value is very close to that of complex . The field
dependence of the magnetization for complex shows that the
experimental data are below the calculated Brillouin curve for
noncoupling SFe and 2SCu spins with g = 2.24 (Inset of Fig. S5 ).
This result further verifies the presence of intrachain Fe(III)-
Cu(II) antiferromagnetic interaction. For complexes , the
Cu(II) ions are in a square pyramidal configuration, where the
unpaired electron lies in the dx orbital. The abnormal Fe(III)-
.
complex
eq. (1).
3 can be described by the spin Hamiltonian operator
4
7
ˆ ˆ
ˆ ˆ
ˆ
(1)
H  2JCuGdSCuSGd 2JFeGdSFeSGd
The data in the whole temperature range of 2-300 K were
fitted by using the MagPack software,18 and the best results are:
JFeGd = -0.341 cm-1, JCuGd = 2.392 cm-1, g = 2.052. This result
indicates the existence of weak antiferromagnetic Fe-Gd
interaction (2JFeGd = -0.49 – -0.84 cm-1)9b,16,19 and moderate
ferromagnetic Cu-Gd interaction,6b,8a,8c,12c,17,20,21 as usual.
†
4
- 7
2
2
-y
Cu(II) antiferromagnetic interaction may be related to the bent
C≡N-Cu bridging mode, which makes the orbital overlap
Complexes 4–6 have, at room temperature, χmT values of
9.96 cm3 K·mol-1
K·mol-1
Cu2LnFe system (Table S3). When the temperature is lowered,
χmT value of complex remains constant down to 100 K and
(4 (5
), 13.97 cm3 K·mol-1 ) and 16.97 cm3
between dx -y of Cu(II) and dxy of low-spin Fe(III) possible.22
Similarly, some cyano-bridged Cu-W/Mo complexes display
abnormal Cu-W/Mo antiferromagnetic interaction due to the
presence of bent Cu-N≡C bridging linkages (138.4-
154.7).8c,12c,23 It is noteworthy that the above-mentioned
abnormal Cu-Fe/Cr/W/Mo antiferromagnetic interaction occurs
to the metal ions where the bridging cyano nitrogen atom is
situated at the axial positions of coordination polyhedral of
Cu(II).
2
2
(6), close to the theoretical values for a non-coupled
4
then increases rapidly to a maximum at 2 K. This behaviour is
associated with the overall ferromagnetic interaction in
complex 4. For complexes 5 and 6, the χmT values increase
gradually with cooling and reach the maximum values at about
6 K before decreasing. In the temperature range of 150-300 K,
the dc magnetic susceptibilities are consistent with the Curie-
Weiss law and give positive Curie-Weiss constants, indicating
the presence of predominant ferromagnetic interactions at high
temperatures. Below 6 K, the rapid decrease of χmT for
The fitting result shows that the phenoxo-bridged Cu(II)-
Gd(III) interaction for complexes
1 and 4 is ferromagnetic and
moderate in magnitude, with the JCuGd values falling in the
range of 1.22-7.38 cm-1 for available phenoxo-bridged Cu(II)-
Gd(III) complexes.20,21 For comparison, structural data and
magnetic properties of phenoxo-bridged CuGd complexes are
collected in Table S4†.6b,12c,20,24 On the basis of the data, we
conclude that the smaller of the dihedral angle of CuO2 and
complexes
5 and 6 might be due to the depopulation of the
Stark sublevels in the Ln(III) ions.
We have approximately fitted the magnetic properties of
complex
4 to a cyclic octanuclear model (Fig. 4) using the
MagPack software18 and the Hamiltonian operator of this model
is described as eq. (2).
GdO2 planes, the greater is JCuGd (Fig. S6†, ESI). Moreover, the
increase of Gu-Gd bond distance and the Gd-O-Cu angle would
simultaneously results in the increase of JCuGd. This conclusion
is consistent with the results based on DFT calculation.25
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
H  2J1(SCu1SGd1  SCu2SGd1  SCu3SGd2  SCu4SGd2
)
(2)
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
2J2 (SFe1SCu2  SFe1SCu3  SFe2SCu1  SFe2SCu4
)
Complex 6
10 Hz
J2
Fe2 Cu
1 J1
Gd1
J2
50 Hz
1.6
1.2
0.8
0.4
0.0
100 Hz
250 Hz
499 Hz
997 Hz
1399 Hz
Cu4
J1
J1
Cu2
J2
Gd2
J1
Cu3 Fe1
J2

Fig. 4 The fitting model of magnetic susceptibility for complex
4
.
In the range of 10-300 K, the best fitting results for complex
are: JGdCu = J1 = 2.945 cm-1, JFeCu = J2 = -0.378 cm-1, g =
3.0
4.5
6.0
7.5
4
T/K
2.078. This result suggests that a weak antiferromagnetic
interaction is present between Fe(III) and Cu(II). The Fe(III)-
Cu(II) ferromagnetic interaction has been reported with few
exceptions.22 To definitely determine the character of Fe(III)-
Cu(II) magnetic coupling in complex 4, we have studied the
magnetic properties of the isostructural complex [Cu2YFe] (7)
Fig. 5 Temperature dependence of the out-of-phase (χ”m) ac
magnetic susceptibilities for complex
6
.
Dynamic magnetic susceptibility. The ac magnetic
susceptibility of complexes 2, 3, 5 and were measured in zero
6
4 | J. Name., 2012, 00, 1-3
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and 2000 Oe dc field (measured frequency was 997 Hz). As
shown in Figs. S7 and S8†, complexes and show no
peaks above 2 K under zero or 2000 Oe dc field. However, the
out-of-phase magnetic susceptibility (χm”) of complex under
2000 Oe exhibit broad frequency-dependent peaks below 3 K
(Fig. 5). The parameter Φ = (ΔTp/Tp)/Δ(logf) = 0.46 is within
the range of normal super paramagnets, precluding the
possibility of a spin glass (0.01< Φ < 0.08). The Arrhenius
equation of τ = τ0exp(Ueff/kT) was employed to extract
parameters that relevant to slow relaxation of magnetism. The
best fitting result is shown in Fig. S9† with τ0 = 1.65×10-6 s and
Ueff = 12.3 K, typical of an SCM.
C25H31.5DyFeN8CuO9.75 (3): C, 34.05; H, 3.60; N, 12.70. Found: C,
DOI: 10.1039/C6NJ01887D
33.58; H, 3.76; N, 12.93. C53H67.5GdFeN12.5Cu2O14 (4): C, 44.09; H,
View Article Online
2
,
3
5
4.71; N, 12.13. Found: C, 43.65; H, 4.83; N, 11.95.
C51H63.5TbFeN11.5Cu2O13.5 (5): C, 43.89; H, 4.59; N, 11.54. Found:
C, 43.81; H, 4.64; N, 11.71. C53H65.5DyFeN12.5Cu2O12.5 (6): C, 44.73;
H, 4.64; N, 12.30. Found: C, 44.61; H, 4.59; N, 12.58.
C48H62YFeN10Cu2O15 (7-4MeCN): C, 44.66; H, 4.84; N, 10.85.
Found: C, 44.70; H, 4.70; N, 10.80.
6
Physical measurements. Elemental analyses (C, H, N) were
performed on an Elementar Vario Cario Erballo analyzer.
Temperature and field-dependent magnetic susceptibility
measurements were carried out on a Quantum Design MPMS-XL5
SQUID magnetometer. And the experimental susceptibilities were
corrected for diamagnetism of Pascal constants. Single-crystal X-ray
data were collected on a Rigaku RAXIS RAPID IP, Bruker
SMART 1000 CCD or SuperNova four-circle diffractometer. The
structure was solved by the direct method (Olex2 1.2 or SHELXS-
2014) and refined by a full matrix least-squares method based on F2
using SHELXL-2014 program.26 Hydrogen atoms were added
geometrically and refined using a riding model. For complex 7, the
hydrogen atoms of the coordinating water were found from the E-
map, and refined isotropically.
Conclusions
Seven new heterotrimetallic complexes have been synthesized.
The 1D zig-zag chain complexes 4-7 can be regarded as a
deformation of octanuclear cyclic structure. Complex
6
(Cu2DyFe) is a single chain magnet and displays field-induced
slow magnetization relaxation. The absence of an single-
molecule magnet property in CuDyFe and CuTbFe trinuclear
complexes would be related to the presence of Fe-Dy/Tb
antiferromagnetic interaction via the cyano bridge,27,28 which is
consistent with the previous assumption that the presence of
cyano-bridged Fe(III)-Ln(III) linkages has a negative effect on
single-molecule magnets.11 Unusual intrachain Cu(II)-Fe(III)
antiferromagnetic interaction is unambiguously present in the
1D complexes, which is likely to originate from the magnetic
orbital overlap via the bent cyanide bridging.
Acknowledgements
This work was supported by the 973 program (2013CB933403)
and the National Natural Science Foundation of China (Project
No. 91222104, 21571113).
Notes and references
Experimental
Materials. All agents were commercially available and used without
further purification.
1
2
3
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26 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr.,
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New Journal of Chemistry
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DOI: 10.1039/C6NJ01887D
Graphic abstract
Ligandꢀdirected assembly of trinuclear and oneꢀdimensional
heterotrimetallic CuIILnIIIFeIII complexes. Unusual antiferromagnetic
CuIIFeIII coupling via cyano bridges
MeiꢀJiao Liu, KongꢀQiu Hu, CaiꢀMing Liu, AiꢀLi Cui and HuiꢀZhong Kou*
Rare phenoxoꢀ and cyanoꢀbridged CuLnFe trinuclear complexes have been prepared.
The 1D Cu2DyFe complex displays both singleꢀchain magnetic property and the
intrachain Cu(II)ꢀꢀꢀFe(III) antiferromagnetic coupling. The presence of FeꢀC≡NꢀLn
bridging linkages goes against the singleꢀmolecule/chain magnetic property of the
complexes.
K3[Fe(CN)6]
O
R = H
O
O
O
Ln
O
N
N
R
R
R
R
O
N
N
Cu
Cu
O
O
K3[Fe(CN)6]
R = CH3
{[Cu(R2valpn)]2Ln}3+ (Ln = Gd, Tb, Dy)