Angewandte
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Heterometallic Complexes
Cyclic Heterometallic Interactions formed from a Flexible Tripeptide
Complex Showing Effective Antiferromagnetic Spin Coupling
Ryosuke Miyake,* Eri Suganuma, Shun Kimura, Hirotoshi Mori, Jun Okabayashi, and
Tetsuro Kusamoto
Abstract: Developing tunable motifs for heterometallic inter-
actions should be beneficial for fabricating functional materi-
als based on cooperative electronic communications between
metal centers. Reported here is the efficient formation of cyclic
heterometallic interactions from a complex containing an
artificial tripeptide with metal binding sites on its main chain
and side chains. X-ray structural analysis and X-ray absorption
spectroscopy revealed that the cyclic metal–metal arrange-
ments arise from the amide groups connecting four square-
planar CuII centers and four octahedral NiII centers in a cyclic
manner. UV/Vis spectral studies suggested that this efficient
formation was achieved by the selective formation of the
square-planar CuII centers and a crystallization process.
Magnetic measurements using SQUID clarified that the
cyclic complex represented the S = 2 spin state at low temper-
atures due to effective antiferromagnetic interactions between
the NiII and CuII centers.
Controlling heterometallic arrangements is desirable when
creating compounds that provide novel functionality based on
electronic communications between metal centers.[1, 4–7] Bio-
logical molecules could provide suitable platforms for direct-
ing these arrangements because their structures can adopt
[*] Dr. R. Miyake, E. Suganuma
Department of Chemistry and Biochemistry, Graduate School of
Humanities and Sciences, Ochanomizu University
2-1-1, Otsuka, Bunkyo-ku, Tokyo 112-8610 (Japan)
E-mail: miyake.ryosuke@ocha.ac.jp
Dr. R. Miyake
JST-PRESTO
4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan)
S. Kimura
Department of Chemistry, Graduate School of Science
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Prof. H. Mori
Department of Applied Chemistry, Faculty of Science & Engineering,
Chuo University
1-13-27 Kasuga, Bunkyo-Ku, Tokyo 112-8551 (Japan)
Dr. J. Okabayashi
Research Center for Spectrochemistry, Graduate School of Science,
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)
S. Kimura, Dr. T. Kusamoto
Department of Life and Coordination-Complex Molecular Science,
Institute for Molecular Science
5-1 Higashiyama, Myodaiji, Okazaki 444-8787 (Japan)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202013373.
Angew. Chem. Int. Ed. 2021, 60, 5179 –5183
Chemie
How to cite: Angew. Chem. Int. Ed. 2021, 60, 5179 – 5183
International Edition: doi.org/10.1002/anie.202013373
German Edition: doi.org/10.1002/ange.202013373
appropriate metal binding sites for targeted arrangements.[2]
In addition, their structural flexibility would cause metal
arrangements to be stimulus responsive using their structural
varieties.[3] Despite this potential, biological compounds are
inefficient at providing through-bond interactions for metal
centers with coordinatively unsaturated sites, which would
signal for their further coordination and are required to
produce an active site for functions such as molecular
recognition, catalysis, and adsorption.[4, 5] Due to uncojugated
parts in their backbone, interactions between metal centers
were formed by either direct connection or connection
through bridging ligands that fill the coordinatively unsatu-
rated sites. For same reason, metal arrangements by biological
molecules have been reported to be linear in many cases.[2]
However, cyclic metallic interactions are more efficient than
linear arrays at producing uniformly conjugated electronic
state from multiple metal centers and providing cooperativity
between each metal center.[6, 7] Therefore, developing such
cyclic metal arrangements using biological molecules could
offer a new method for designing sophisticated functions
based on electronic interactions at metal centers. We envi-
sioned that peptides could provide square-planar coordina-
tion sites that connect metal centers through their amide
groups[8] by designing metal binding sites on both the side
chains and main chain (Figure 1). We previously reported an
artificial tripeptide (1)[9] that would be suitable for the present
study, as it forms a cyclic complex ([(1-3H+)4Ni8]4+, 1-Ni8)
with two different NiII centers (octahedral and square-planar)
connected by amide groups. Herein, we report the efficient
formation of cyclic heterometallic arrangements through
peptide amide groups that link the electron orbitals of CuII
and NiII metal centers, as well as their coordinating sites. This
complex exhibited the desired heterometallic interactions,
and we observed efficient antiferromagnetic (AFM) spin
coupling (J/kB  25 K) in the cyclic connections of the
square-planar CuII centers (S = 1/2) and the octahedral NiII
centers (S = 1).
Figure 1. Conceptual Figure showing the formation of the cyclic CuII–
NiII arrangement using a flexible peptide ligand.
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Tripeptide ligand 1 possesses tridentate metal-coordina-
tion sites on its side chains (red and blue in Figure 2 a) that
form an octahedral metal center and a tetradentate binding
site on its main chain (green in Figure 2 a) that forms a square-
planar metal center. The tripeptide was synthesized[9] and
then mixed with equivalent amounts of Ni(ClO4)2·6 H2O and
Cu(ClO4)2·6 H2O and 3 equiv of NaHCO3 to successfully
produce cyclic CuII-NiII complex [(1-3H+)4Cu4Ni4]4+ (1-
Cu4Ni4) as purple, needle-like crystals in 78 % yield.[10]
A single crystal suitable for X-ray structural analysis was
obtained by recrystallization from water, and single crystal X-
ray structural analysis[11] and X-ray absorption spectroscopy
(XAS) measurements revealed that 1-Cu4Ni4 possessed four
square-planar CuII centers and four octahedral NiII centers
that were cyclically connected to each other through the
amide groups. This octa-nuclear complex was formed by four
deprotonated 1 (1-3H+) molecules coordinating with the
square-planar metal centers that connect at the tridentate
binding sites to give an octahedral metal center. The
coordination bond lengths further supported that the result-
ing structure was octanuclear complex 1-Cu4Ni4. The N M
bonds of the square-planar center were 1.87–2.06  (avg.
1.95 ), which were longer than those observed in the 1-Ni8
complex (1.84–1.94 , avg. 1.88 ),[12] while those of the
octahedral centers of both complexes were almost identical
(Figure 2 b and Table S5 in the Supporting Information). In
each octahedral center, uniaxial elongation (Jahn–Teller
distortion specific for CuII center) was not observed, suggest-
ing the existence of NiII ions in the sites. The assignment of
metal centers is consistent with that established by XAS
measurements (refer to Figure 4 and discussion below). For
each CuII center, deprotonated amide groups and terminal
amino groups were connected to form square-planar coor-
dinates. The CuII centers were connected to neighboring
octahedral NiII centers through the amide groups of 1 with
distances of 5.63–5.80 , while the Ni-Ni and Cu-Cu distances
were 7.61–7.73  and 10.02–10.14 , respectively. Further-
more, crystalline water molecules were weakly coordinated to
one of the four CuII centers, which distorted the square-planar
geometry and suggested the possibility of extra coordination
Figure 2. a) The reaction Scheme for forming the CuII–NiII complex with tripeptide 1 and its structure (possible metal-metal interaction pathway is
shown as an orange line, and the metal binding sites on the main chain are colored green and those at the side-chain are red and blue).
b) Comparison of the bond lengths in 1-Cu4Ni4 and 1-Ni8 (for details of bond length: see Table S5). c) The packing structure of the complex.
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to this CuII center. A pair of these cyclic complexes with the
distorted square-planar CuII centers form an asymmetric unit
in the crystal packing structure, giving huge crystal units
(monoclinic P21, ca. 11  31  33 ). In the crystal packing
structure, the cyclic complexes are closely faced at all CuII
centers except the distorted ones (distance between CuII
centers: 3.79–3.92 , for details, see Figure S11). As
a result, relatively large cavities were formed in the crystal
that were filled with crystalline water molecules (Figures 2 c,
S9,10).
Moreover, a different needle-like crystal of 1-Cu4Ni4 was
observed when analyzing the crystals in a saturated solution
using a microscope[13] (for detailed crystalline structure, see
Figures S7—S9), which suggested that the weakly coordi-
nated water molecules at the CuII center could be removed by
small changes in the surrounding environment.
It is notable that the 1-Cu4Ni4 complex was also obtained
even when the ratio of Cu(ClO4)2·6 H2O/ Ni(ClO4)2·6 H2O was
different from 1 in the mixture of starting materials. 1-Cu4Ni4
was obtained from the mixture containing 1 equiv of Cu-
(ClO4)·6 H2O and 2 equiv of Ni(ClO4)·6 H2O per 1 equiv of
1 as well as the mixture using the opposite ratio of Cu/Ni
(yield: 27, 54 % respectively). In addition, when the sum of
the mol number of Cu(ClO4)2·6 H2O and Ni(ClO4)2·6 H2O is
less than two times the mol number of 1, 1-Cu4Ni4 was
selectively obtained in good yield (above 80 % based on mol
number of Ni(ClO4)2·6 H2O) even if the ratio of CuII/NiII is 5
(Table S1). It is notable that 1-Cu4Ni4 was also synthesized
from 1-Ni8 by mixing with 4 equiv of Cu(ClO4)2·6 H2O per
1 equiv of 1-Ni8 in solution state.[14]
This transformation process from 1-Ni8 to 1-Cu4Ni4 was
studied by using UV/Vis and mass spectral studies. As shown
in Figure 3 a, after adding Cu(ClO4)2·6 H2O, the absorption
peak of 1-Ni8 (ca. 430 nm) typical of square planar NiII center
with deprotonated amide groups,[8c] decreased upon addition
of ca. 4 equiv of CuII ions per 1 equiv of 1-Ni8. This spectral
change accompanied the increase of the peaks around 530–
550 nm, which is the region of the absorbance of the square-
planar CuII center with deprotonated amide groups.[8d] Con-
sidering that the absorption band of octahedral NiII center
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Figure 3. UV/Vis spectra of a) 1-Ni8 and the its solution mixture with
ca. 1, 2, 3, 4 equiv of Cu(ClO4)2·6 H2O, b) 1-Cu4Ni4 (purple line), 1-Ni8
(red line), and Cu(ClO4)2·6 H2O (blue line), and (inset of b) 1-Cu4Ni4 in
solution (red line) and in the solid state (blue line) at 25 8C. [1-
Cu4Ni4] = [1-Ni8] = [Cu(ClO4)2·6 H2O] = 3.9 mM/ metal units.

was observed around 550 nm,[15] these spectral changes

indicated the replacement of NiII ions with CuII ions at the
square-planar center. The assignments of the absorbance
were supported by DFT calculations. This replacement was
also supported by the ESI-TOF mass spectral study of 1-Ni8
Figure 4. X-ray adsorption spectroscopy of 1-Cu4Ni4 at room temper-
by mixing with CuII ions (for details, see the additional
ature in the a) Ni K-edge range and b) Cu K-edge, each with compar-
discussion in the Supporting Information and Figure S2). isons to those of metal foil and 1-Ni8.
Thus, the selective coordination of CuII to the square-planar
centers should be key for the efficient formation of the cyclic
heterometallic arrangement (i.e., 1-Cu4Ni4) using 1. This cyclic heterometallic arrangement present in the original
discussion is consistent with the fact that 1-Cu4Ni4 was mostly sample remained intact in the dried sample and does not
maintained in solution state, which was suggested by the drastically change with temperature.
similarity of the absorption peaks in its solution and solid To clarify the through-bond interactions in the arrange-
states (inset of Figure 3 b). This is also supported by ESI-TOF ment, we compared the magnetic behavior of 1-Cu4Ni4 and 1-
mass spectrum of crystalline 1-Cu4Ni4 in a methanol solution, Ni8 under dry conditions (Figures 5 and S23). Temperature-
which showed a signal at m/z = 635 ([(1-3H+)4Cu4Ni4- dependent magnetic susceptibilities (c–T behaviors) were
(ClO4)]3+) (Figure S5). It is notable that the further replace-
ment or coordination to 1-Cu4Ni4 was suggested under the
existence of excess CuII or NiII ions (> 4 equiv) in the solution
state (Figures S3 and S4), indicating that crystallization
process is essential for obtaining pure 1-Cu4Ni4 from the
mixture solutions.
It is notable that the peak at ca. 530 nm[16] showed a slight
red-shift (Figure S21) in the UV/Vis spectrum of the solid
sample upon lowering the temperature, indicating the tem-
perature dependency of the electronic properties of this cyclic
heterometallic arrangement.
Due to the large cavities formed in the crystals, which
mentioned above, the crystals of 1-Cu4Ni4 easily lose their
crystallinity during the drying process and broadened their
powder diffraction patterns (Figure S17). This indicated that
the crystalline packing structure was partially altered by the
removal of crystalline water molecules. Thus, an air-dried
crystalline sample was characterized by XAS, which revealed
a square-planar CuII center and the ratio of CuII/NiII ions to be
ca. 1 (Figures 4, S18,19). X-ray absorption near edge structure
(XANES) displayed an intense, pre-edge peak at  8986 eV Figure 5. Magnetic properties of 1-Cu4Ni4 and 1-Ni8 : cT–T plots at 1 T
for 1-Cu4Ni4, which is characteristic of CuII ions with square- for a) 1-Cu4Ni4 and b) 1-Ni8 ; and M-H curves at 2 K for c) 1-Cu4Ni4 and
planar (or pyramidal) symmetry[17] (Figure 4). A similar peak d) 1-Ni8. Dashed lines in (a) are simulated curves based on the cyclic
heterospin model with J/kB values of 20 (red), 22.5 (green), 25
was not observed for NiII ions with a D4h point group
(purple), and 30 (black) K. Black line in (c) indicates Brillouin
symmetry (  8336 eV[18]), but it was seen in the 1-Ni8 function for S = 2. Dotted lines in (c) and (d) indicate the quadruple of
spectrum. The spectra of 1-Cu4Ni4 taken at 300 K and 10 K the Brilluon function for S = 1/2 (c) and S = 1 (d). For details of the
(Figure S19) were almost identical, suggesting that the basic simulation, see the Supporting Information.

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Communications
analyzed based on the Curie–Weiss law. Estimated Weiss
temperatures indicated efficient AFM interaction taking
place between the spin in 1-Cu4Ni4 (q = 44 K) while it was
very small in 1-Ni8 (q = 0.87 K). Simulation of the cT–T plot
of 1-Cu4Ni4 based on the cyclic heterospin model (Figure 5 a)
also suggested a through-bond CuII-NiII AFM coupling with J/
kB  25 K (for details, see Supporting Information). Field-
dependent magnetization curve (M-H curve) at 2 K of 1-
Cu4Ni4 could be represented by Brillouin function for S = 2
with g = 2.10 (g-value was estimated by ESR spectroscopy in
Figure S24), suggesting that the spins in adjacent CuII and NiII
centers interacted antiferromagnetically in the cyclic struc-
ture to yield a ferrimagnetic Stotal = 2 spin state at this
temperature. This Stotal value also guarantees the structural
assignment of 1-Cu4Ni4 since the value can be obtained only
from the cyclic alternating arrangement of four square-planar
CuII centers (S = 1/2) and four octahedral NiII centers (S = 1)
with CuII-NiII AFM coupling. The M-H curve of 1-Ni8
indicated existence of four S = 1 spins with small AFM
interaction. These results show distinct AFM coupling in 1-
Cu4Ni4.
The AFM coupling in 1-Cu4Ni4 is likely attributed to
indirect overlap of the dx2 y2 orbital of the CuII center and the
dz2 and/or dx2 y2 orbital of the NiII center via the amide group
(i.e., superexchange mechanism). On the other hand, negli-
gible spin-spin interaction in 1-Ni8 is interpreted as a result of
large separation of the paramagnetic NiII centers owing to an
alternating arrangement of the octahedral NiII (S = 1) and
square-planar NiII (S = 0) centers in the cyclic structure.
The simulated cT–T curves matched with the cT–T plot of
1-Cu4Ni4 moderately but not completely even changing the J/
kB and g values or introducing a J2 term in the magnetic model
(Figure 5 and S25). The incomplete matching may be
attributed to temperature-dependent heterometallic interac-
tion, as suggested by the temperature-dependent UV/Vis
spectrum.[19]
In conclusion, we succeeded to synthesize a cyclic hetero-
metallic arrangement (1-Cu4Ni4) where the amide groups of
tripeptide 1 bound the CuII and NiII ions through coordinating
sites on the side chains and the main chain, respectively.
Magnetic studies revealed effective AFM interactions
between the square-planar CuII and octahedral NiII centers.
By the tripeptide complex, effective through-bond hetero-
metallic interactions were achieved for square-planar metal
centers, which is useful for allowing extra coordination. It is
rare to observe such through-bond metal-metal interactions
supported by flexible frameworks, and considering the facile
design and structural flexibility of peptides, this approach
could be applied to generating heterogeneous cyclic metal
arrays for various combinations of metal ions. Therefore, our
findings provide a new method for designing various functions
through fine-tuning electron properties with metal-metal
interactions.
Acknowledgements
This research was supported by JST, PRESTO
(JPMJPR151A to R.M.) and JSPS KAKENHI (20K05539
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to R.M., JP20H02759 to T.K.). A part of this work was
conducted in Institute of Molecular Science, supported by
Nanotechnology Platform Program “Molecule and Material
Synthesis” of the Ministry of Education, Culture, Sports,
Science and Technology (MEXT), Japan. Parts of the
synchrotron radiation experiments were performed under
the approval of the Photon Factory Program Advisory
Committee, KEK (No. 2019G029). We thank Prof. Shuichi
Hiraoka (The University of Tokyo) and Dr. Yasuyuki
Yamada (Nagoya University) for fruitful discussions. We
also thank Dr. Kenji Yoza (Bruker A.X.S) for assistance with
X-ray structural analysis.
Conflict of interest
The authors declare no conflict of interest.
Keywords: heterometallic complexes · metal–
metal interactions · peptides · structure elucidation ·
through-bond interaction
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of its crystalline structure, see the Supporting Information.
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[19] Other possibilities, such as simplicity of the magnetic model and
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Manuscript received: October 4, 2020
Accepted manuscript online: November 18, 2020
Version of record online: January 18, 2021
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