Controlled and Reversible Stepwise Growth of Linear Copper(I) Chains Enabled by Dynamic Ligand Scaffolds

Article abstract of DOI:10.1002/anie.201709167

Reversible stepwise chain growth in linear Cu^I assemblies can be achieved by using the dynamic, unsymmetric naphthyridinone-based ligand scaffolds L1 and L2. With the same ligand scaffolds, the length of the linear copper chain can be varied from two to three and four copper atoms, and the nuclearity of the complex is easily controlled by the stepwise addition of a Cu^I precursor to gradually increase the chain length, or by the reductive removal of Cu atoms to decrease the chain length. This represents a rare example of a stepwise controlled chain growth in extended metal atom chains (EMACs). All complexes are formed with excellent selectivity, and the mutual transformations of the complexes of different nuclearity were found to be fast and reversible. These unusual rearrangements of metal chains of different nuclearities were achieved by a stepwise “sliding” movement of the naphthyridinone bridging fragment along the metal chain.

Full text of DOI:10.1002/anie.201709167

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Accepted Article
Title: Controlled and reversible stepwise growth of copper(I) linear
chains enabled via dynamic ligand scaffolds
Authors: Orestes Rivada-Wheelaghan, Sandra L. Aristizábal, Joaquín
López-Serrano, Robert R. Fayzullin, and Julia Khusnutdinova
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709167
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10.1002/anie.201709167
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Controlled and reversible stepwise growth of copper(I) linear
chains enabled via dynamic ligand scaffolds
Orestes Rivada-Wheelaghan,[a] Sandra L. Aristizábal,[a] Joaquín López-Serrano,[b] Robert R.
Fayzullin,[c] and Julia R. Khusnutdinova*[a]
Abstract: Reversible stepwise chain growth in linear CuI assemblies
can be achieved using dynamic, unsymmetrical naphthyridinone-
based ligand scaffolds L1 and L2. Using the same ligand scaffolds,
the linear copper chain length varies from 2, 3 to 4 copper atoms
and the nuclearity of the complex is easily controlled by the stepwise
addition of a CuI precursor to gradually increase the chain length, or
by the reductive removal of Cu atoms to decrease the chain length.
This represents a rare example of a stepwise controlled chain
growth in extended metal-atom chains (EMAC). All complexes are
formed with excellent selectivity and the mutual transformations of
the complexes of different nuclearity were found to be fast and
reversible. These unusual rearrangements of the metal chains of
different nuclearities are achieved by stepwise “sliding” of the
naphthyridinone bridging fragment along the metal chain.
their properties, and therefore, fine control over the selective
formation of solution-stable polynuclear metal chains of defined
lengths and geometry is needed, especially in the case of labile
complexes of late first row transition metals such as CuI.[8]
In the case of simple bridging ligands such as carboxylates,
although polymetallic CuI clusters of different nuclearities could
be formed, the geometry of these complexes was difficult to
predict and their stability was mostly limited to the solid state.[8a]
Another method that provides better control over the
geometry and nuclearity of 1D multimetallic chains is the direct
combination of polynucleating multidentate ligands (e.g. oligo-
pyridylamides) with a metal precursor yielding in one step EMAC
9]
complexes (some examples in Scheme 1).[2b, In this case,
symmetrical polynucleating ligand scaffolds that can bind a pre-
defined number of metal atoms in a chain are typically used.
However, in order to vary the metal chain length, elaborate
synthesis of new ligand scaffolds is usually required. At the
present moment, examples of well-defined CuI chains containing
three,[10] four[9a, 11] or more[12] Cu atoms are still rare.
The above methods describe bottom-up syntheses with
metal precursors and ligands. To our knowledge, examples of
dynamic interconversion between linear chains of different
nuclearities have not been reported, although examples of
reversible interconversion of polynuclear complexes of different
geometries are known (i.e. metal clusters involving non-linear
metal assemblies).[13]
Linear chain multimetallic complexes remain an active area of
research due to their applications as supramolecular building
blocks, and their ability to undergo multiple electron transfer
steps that play an important role in catalysis and small molecule
activation.[1] Furthermore one-dimensional (1D) assembly of
transition-metal complexes (“molecular wires”) is of high interest
for molecular microelectronics applications and studying
processes of electron transfer in metal chains.[2] Multinuclear Cu
complexes were among the first structurally characterized and
studied extended metal atom chain (EMAC) compounds.[2b, 3] In
addition, CuI “wires” and clusters of various nuclearities have
been shown to have interesting photophysical properties that
make them suitable for optoelectronics applications.[4] CuI
polynuclear species have also been utilized as precursors in the
synthesis of metal-rich materials in microelectronics[5] and as
tunable dopants in OLEDs.[6] Recently, theoretical studies
indicated that multicopper coordination to DNA base pairs may
improve conductivity of DNA-based “nanowires”.[7]
The nuclearity of such complexes has a significant effect on
Scheme 1. Examples of polynucleating ligands for the formation of metal
chain complexes.
[a]
[b]
[c]
Dr. O. Rivada-Wheelaghan, S. L. Aristizábal, Prof. J. R
Khusnutdinova
Coordination Chemistry and Catalysis Unit
Okinawa Institute of Science and Technology Graduate University
1919-1 Tancha, Onna-son, Okinawa, Japan 904-0495
E-mail: juliak@oist.jp
In this work, we developed the new unsymmetrical dynamic
ligand scaffolds L1 and L2 (Scheme 1), in which the
naphthyridinone framework can be used as a versatile bridging
fragment, capped with bis- or mono-picolyl amine units. We
showed that the same ligand scaffolds can be used to assemble
mono-, bi-, tri-, and in case of L1 tetrametallic CuI complexes in
a selective and reversible manner. Stepwise and reversible
growth of the metal chain was achieved by adding the required
equivalents of a CuI precursor, leading to the selective formation
of only one product, with nuclearity changing gradually from 1 to
4. In the reverse building-down process, removal of CuI atoms
by their chemical reduction leads to a decrease of the metal
chain length in a selective manner. Controlled formation of metal
Dr. J. López-Serrano
Departamento de Química Inorgánica, Instituto de Investigaciones
Químicas (IIQ), and Centro de Innovación en Química Avanzada
(ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de
Investigaciones Científicas (CSIC), Av. Américo Vespucio 49, Isla
de la Cartuja, 41092 Seville (Spain)
Dr. R. R. Fayzullin
A.E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Scientific Center, Russian Academy of Sciences
Arbuzov Street, 8, Kazan, 420088, Russian Federation
Supporting information for this article is given via a link at the end of
the document.
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chains with the same ligand scaffold simplifies the synthesis and
the isolation of a polymetallic complex.
Moreover, reversible and selective transformations between
CuI linear chains of different nuclearity can be achieved by
varying only the solvent polarity. Such reversible chain growth
and interconversion between complexes of different nuclearity is
possible due to the versatile nature of the unsymmetrical ligand
scaffold that is capable of dynamic changes in denticity and
coordination mode.
Figure 1. ORTEP of 1a, 1b, 2a, 2b, 2b’, 3a·BArF, 3b·BArF, and 4a∙BArF
,
2
respectively, at 50% probability level.[14] The structures of 3a·BF4, 3b·BF4 are
present in SI. Counterions, hydrogen atoms (except for NH), and solvent
molecules are omitted for clarity. For 2b only one of two symmetrical
independent molecules is depicted. In the case of 2b’ π-stacking of 2-picolyl
arms of the independent molecule A and the symmetrical equivalent of the
molecule B (1–x, –1/2+y, 2–z) is shown: centroid to centroid distance is
3.5979(17) Å, plane shift is 0.999(5) Å
Scheme 2. Stepwise formation and interconversion of multinuclear CuI chain
complexes.
The ligands L1 and L2 were obtained in 70-80% yields by
the reaction of 7-choro-1,8-naphthyridine-2(1H)-one with the
corresponding secondary amine.[15] Treatment of neutral ligands
L1 or L2 with 1 eq. of CuCl in methanol yielded the mononuclear
complexes 1a, [CuCl(L1)], and 1b, [CuCl(L2)] in high yields
(Scheme 2, step A). The structures of 1a and 1b were confirmed
by single crystal X-ray diffraction analysis, which also revealed
hydrogen bonding between the uncoordinated NH group of the
naphthyridinone and the chloride ligand (see Fig. 1).[14]
Subsequent NH group deprotonation in complexes 1a and 1b in
the presence of Cs2CO3 in MeCN triggered formation of the
binuclear neutral complexes 2a, [Cu(L1)]2, and 2b, [Cu(L2)]2,
respectively, although 2a was obtained in low yield. Alternatively,
selective formation of 2a in higher yield was achieved by simple
treatment of L1 with 1 equiv. of [Cu(MeCN)4][BF4] in the
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presence of Cs2CO3 (Scheme 2, step B). NMR spectroscopy of
2a and 2b confirms their symmetrical structure in solution and
the absence of the NH proton. Accordingly, X-ray analysis of the
single crystals grown from THF solutions shows that both
complexes 2a and 2b contain a symmetrical Cu…Cu core
bridged by nitrogen atoms of two deprotonated naphthyridinone
fragments, while the oxygen atoms remain unbound (Fig. 1). Cu-
Cu bond distance in 2a and 2b is in the range of 2.649 to 2.696
Å, somewhat shorter than the sum of the van der Waals radii
(2.80 Å).[1a] Notably, Cu-N(amine) distances in 2a and 2b are
longer (2.391-2.492 Å) than Cu-N distances between a metal
and pyridine or naphthyridinone nitrogens (1.979-2.117 Å),
which could potentially contribute to the dynamic behavior of
these systems (vide infra).
Interestingly, when crystals of 2b were grown from less polar
solvent, toluene, an unsymmetrical structure 2b’ was obtained
(Fig. 1) in which shorter Cu-Cu distances are present (2.541 and
2.557 Å), and one of the copper atoms is coordinated only to two
naphthyridinone N-donors, with one of the capping picolyl-amine
unit completely unbound. In the crystal structure, intermolecular
π-stacking interaction between free picolyls of two binuclear
units is (Fig. 1).
remain uncoordinated, suggesting that further extension of the
metal chain may still be possible.
We were delighted to see that the treatment of 3a·BArF with
another equivalent of [Cu(MeCN)4][BArF] in THF quantitatively
yielded a new dicationic species 4a·BArF , [Cu4(L1)2][BArF]2
2
(Scheme 2, step D). This tetranuclear complex had distinct
features in solution NMR and UV/Vis spectra as compared to
3a·BArF. In particular, an absorption band was present in UV/Vis
spectrum in THF at 342 nm (ε = 32,000 M-1cm-1) that was not
observed in binuclear or trinuclear species. Single crystals were
obtained from THF solution, and X-ray analysis revealed a
tetranuclear linear Cu4 core with Cu-Cu distances of 2.504 and
2.534 Å (Fig. 1). The two central Cu atoms feature distorted
square planar geometry. Comparison of structures of 2a, 3a and
4a reveals that as the chain length increases, the
naphthyridinone fragment is “sliding” along the metal chain (see
TOC).
The two terminal Cu atoms are bound to one N-atom of
naphthyridine and are stabilized by coordination to amine as well
as to both pyridines of the bis-picolylamine capping unit. The
absence of such tetranuclear complex in the case of complex 3b
with monopicolyl ligand L2 indicates that the presence of the
additional picolyl arm in L1 played an important role in the
assembly of four copper atoms in a linear chain. All complexes
2a-b, 3a-b·X, 4a·X2 were isolated in high yields and fully
characterized by NMR, UV/Vis and FT-IR spectroscopy,
elemental analysis and X-ray diffraction.[14-15] ESI-MS also
confirms the existence of binuclear and trinuclear species in
polar solvents, demonstrating that these species are viable in
solution and not only in the solid state.
Gas phase DFT[16]-optimized geometries of 2b and 2b’ are in
good agreement with the spectroscopic and X-ray diffraction
data. The calculations indicate that the symmetrical structure is
less stable by a mere 1.2 kcal mol-1. The free energy difference
becomes smaller in THF (0.2 kcal mol-1) than in toluene (0.6 kcal
mol-1), though the relative stability is not reversed. Regardless,
both structures are almost isoenergetic and solvent stabilization
does not need to be invoked to explain the facile opening of the
picolylamine capping unit.
The selectivity of the multimetallic metal assembly can be
demonstrated by solution NMR titration experiment. Stepwise
addition of [Cu(MeCN)4][BArF] to a solution of 2a in THF-d8,
showed initial selective formation of 3a·BArF, followed by
subsequent formation of 4a·BArF2 (Fig. 2).
Such facile opening of the picolylamine capping unit leading
to a coordinatively unsaturated copper center prompted us to
study the possibility of further metal chain growth. To our
satisfaction, when 1 equiv. of [Cu(MeCN)4][X] (X = BF4 or BArF;
BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) was added
to a solution of 2a or 2b in THF (X = BArF) or MeCN (X = BF4),
new monocationic complexes 3a·X, [Cu3(L1)2][X], and 3b·X,
[Cu3(L2)2][X], respectively, were obtained that had distinct
solution NMR and UV/Vis characteristics (Scheme 2, step C).
The reaction occurred within seconds at 20 ⁰C and only the final
1
products could be observed by H NMR spectroscopy after CuI
addition. The identity of the counter-anion did not affect solution
NMR spectra, while some broadening was observed in the NMR
spectra of 3a-b·BArF in CD3CN solvent as compared to spectra
in less coordinating THF-d8, which indicated that ligand
coordination retains some dynamics. X-ray structures of 3a·X
and 3b·X confirmed a linear assembly of three Cu atoms, with
Cu-Cu distances in
a range of 2.501-2.611 Å (Fig. 1).
Interestingly, the naphthyridinone ligand framework now acts as
a trinucleating bridging fragment binding to trinuclear copper
core through both N-atoms as well as one O-atom,
demonstrating that naphthyridinone acts as a bridging ligand of
variable denticity. In both 3a·X and 3b·X, the central Cu atom
has an almost square planar geometry. Similar to binuclear
species, in both 3a·X and 3b·X, the Cu-N(amine) bond is longer
(2.202-2.251 Å) than Cu-N bonds with pyridines and
naphthyridinone (1.882-2.152 Å).The second picolyl arm in 3a·X
Figure 2. Stepwise formation of multinuclear Cu chains in solution observed
by 1H NMR in THF-d8 solution at 20 ⁰C during sequential addition of CuI.
Bottom: initial spectrum of 2a; middle: spectrum after addition of 1 equiv. of
[Cu(MeCN)4][BArF] to 2a; top: after addition of total
[Cu(MeCN)4][BArF] to 2a.
2
equiv. of
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Not only chain growth, but also chain shortening can be
achieved in a selective manner. Thus, switching to a different
solvent also leads to reversible transformations between the
tetra- and trinuclear Cu core. Dissolving isolated 4a·BArF in
2
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2.
removed via chemical reduction. Thus, treating 3a·BArF and
3b·BF4 with 1.2 equiv of cobaltocene Cp2Co led to precipitation
of metallic copper and selective formation of the corresponding
binuclear complexes 2a and 2b as the only products present in
solution in 50% and 72% yields, respectively (Scheme 2, step F).
To our knowledge, this is the first example for a controlled
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rearrangement di-, tri- and tetranuclear Cu chain complexes.
This is enabled by stepwise “sliding” of the bridging fragment
along the metal chain. By contrast to previously reported
examples where ligand design specific to each chain length is
required, the same ligand can support a variety of chain lengths,
depending on solvent polarity and stoichiometry. This is a rare
example of a stepwise selective chain growth in a linear metal
chain compound. Such ligand design can be useful in
developing applications of multicopper complexes as flexible
supramolecular building blocks and switches of variable metal
chain length in a simple and selective manner. The principle of
ligand design described in this work can potentially be expanded
to support polynuclear systems that include various kinds of
metal centers by modification of the capping chelating group to
include soft or hard donors of suitable geometry, or by
modification of the heterocyclic framework. Moreover, stepwise
formation of polymetallic species in combination with careful
adjustment of the capping fragment coordination properties may
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selectively incorporate two kinds of metals in the terminal and in
the central positions, an area we are currently investigating.
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Acknowledgements
O.R.-W. is a JSPS International Research Fellow. The authors
thank Mr. A. Villar-Briones and Dr. M. Roy for performing HR-MS
analysis and acknowledge OIST for full funding of the project.
J.L-S. acknowledges the use of computational facilities of the
the supercomputing center of Galicia (CESGA) and of the
Centro de Servicios de Informática y Redes de Comunicaciones
(CSIRC) of the Universidad de Granada (UGR).
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Keywords: copper • chain structures • ligand design • reversible
[14] CCDC 1571963 (1a), 1571964 (1b), 1571965 (2a), 1572036 (2b),
1571966 (2b'), 1571967 (3a·BArF), 1571968 (3a·BF4), 1571970
(3b·BArF), 1571971 (3b·BF4), and 1571972 (4a·BArF2) contain the
supplementary crystallographic data for this paper. These data are
provided free of charge by The Cambridge Crystallographic Data
Centre.
interconversion • stepwise growth
[1]
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Liddle), Wiley-VCH, Weinheim, Germany, 2015, pp. 397-428; b) R. C.
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[15] See the Supporting Information.
[16] Calculations carried out at the DFT wB97XD/6-311g(d,p)+SDD level
with the Gaussian09 software. See the SI for the full references and
additional details.
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Copper chain traffic control: Stepwise
growth in copper(I) linear chain
complexes is achieved through
dynamic ligand scaffolds. Complexes
containing the same ligand and one,
two, three or four CuI atoms
Orestes Rivada-Wheelaghan, Sandra L.
Aristizábal, Joaquín López-Serrano,
Robert R. Fayzullin, and Julia R.
Khusnutdinova*
Page No. – Page No.
interconvert reversibly and selectively
controlled by stoichiometry, solvent
polarity and redox transformations.
Controlled and reversible stepwise
growth of copper(I) linear chains
enabled via dynamic ligand scaffolds
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