Formation of an interlocked double-chain from an organic-inorganic [2]rotaxane

Article abstract of DOI:10.1039/c8cc09339c

Here we show that a structure containing a polymeric interlocking daisy chain is obtained from the reaction of an inorganic-organic [2]rotaxane [HB{CrIII7Ni^II(μ-F)₈(O₂C^tBu)₁₆}], where B is an organic thread terminated with a bi-pyridyl unit, with an oxo-centered metal carboxylate triangle [FeIII2Co^II(μ₃-O)(O₂C^tBu)₆(HO₂C^tBu)₃].

Full text of DOI:10.1039/c8cc09339c

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Commun., 2019, DOI: 10.1039/C8CC09339C.
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Formation of an Interlocked Double-Chain from an Organic-
Inorganic [2]Rotaxane
a,b
a,c
a
a
Jesús Ferrando-Soria, Antonio Fernandez, Iñigo j. Vitorica-Yrezabal, Deepak Asthana,
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
Christopher A. Muryn, Floriana Tuna, Grigore A. Timco and Richard E. P. Winpenny*
DOI: 10.1039/x0xx00000x
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Here we show that a structure containing a polymeric interlocking Here we report an interlocked [c2]-daisy chain based on hybrid
1
5
daisy chain is obtained from the reaction of an inorganic-organic organic-inorganic rotaxanes. The term molecular daisy chain,
[
2]rotaxane [HB{CrIII
II
t
7 8 2
Ni (μ-F) (O C Bu)16}], where B is an organic first coined by Stoddart, refers to mechanically interlocked
thread terminated with a bi-pyridyl unit, with an oxo-centered polymers, originally containing organic components.
III
II
t
t
metal carboxylate triangle [Fe
2
Co (μ
3
-O)(O
2
C Bu)
6
(HO
2
C Bu)
3
].
First, we synthesised a hybrid organic-inorganic [2]rotaxane
from the reaction of CrF
3
.4H
2
O
with [Ni
2
(μ-OH
2
)
1
The development of supramolecular chemistry and self-
CtBu)
t
16
(O
2
4
(HO
2
C Bu)
4
]
in
the
presence of
(4'-
2
assembly methodologies has led to many mechanically
interlocked molecules (MIMs). The initial interest in MIMs,
focused on catenanes, rotaxanes and knots, was based on
their beauty and structural complexity. This has evolved into a
quest for new synthetic methodologies to obtain MIMs
phenethylamino)methyl-1,1'-biphenyl-4-ol (A) (6:2:1 molar
ratio) using pivalic acid as solvent (Figure 1a). This produces a
3
4
5
6
[
[
2]rotaxane where the organic axle is terminated by a phenol
HA{Cr Ni (μ-F) (O C Bu)16}] (1), whose X-ray crystal structure
7 8 2
III
II
t
could be solved (Figure S11). A Steglich esterification reaction
7
extended into 1D-, 2D- and even 3D-arrays, where the
structural complexity might lead to applications. To this end we
between 1 and 3,5-bis(pyridin-4-ylethynyl)benzoic acid gives
8
III
II
t
the key [2]rotaxane [HB{Cr
7 8 2
Ni (μ-F) (O C Bu)16}] (2), hereafter
have performed
a reaction involving two polymetallic
abbreviated as {Cr Ni-Py } (2). This [2]rotaxane has two widely
7
2
compounds – an octametallic wheel and a oxo-centred metal
triangle, and we find a highly complex interlocked structure.
We have been studying cyclic polymetallic complexes of
space N-donor groups in a predefined Y-type geometry (see
ESI). The phenyl group that terminates one end of the axle is
7
sufficiently large that the {Cr Ni} wheels cannot dethread; 1 and
t
formula [Cation][Cr
7
MF
8
(O
2
C Bu)16] (M = a divalent metal ion) in
2
are therefore rotaxanes not pseudo-rotaxanes. Crystals of 2
…
which the metal metal edges are bridged by two pivalate
) external to the ring or wheel, and a fluoride
inside the wheel. Our explorations have included synthesis of
were grown but do not diffract to give a high-resolution
structure.
t
–
groups ( Bu-CO
2
9
Compound 2 was reacted with an oxo-centred triangle,
1
0
11
hybrid organic-inorganic rotaxanes, daisy-chains, large
III
II
t
t
17
[
{
Fe
Fe
2
Co (μ
3 2 6 2 3
-O)(O C Bu) (HO C Bu) ], hereafter abbreviated as
1
2
13
molecular nanoparticles, and coordination polymers. Use of
pivalate has many advantages. The first is that it ensures high
solubility in non-polar solvents, avoiding thus solvent
2
Co}, in acetone at 50 °C for 1 hour (1.5:1 molar ratio). The
solution was evaporated and the residue recrystallized from
THF/MeCN (3:1 ratio). Analysis showed the formation of a
…
competition in reactivity. Pivalate also maximizes CH HC
III
II
t
III
II
structure of formula [[HB{Cr
O)(O C Bu) (HO C Bu) ]
2 6 2 3 2
7
Ni (μ-F)
] (3) (Figure 1b).
The asymmetric unit of compound 3 consists of three {Cr
Py } rotaxanes and two {Fe Co} triangles (Figure 2). The
secondary building unit of the structure is a hinged macrocycle
containing four triangles and four {Cr Ni-Py } rotaxanes (Figure
2a and S12). There are two pairs of triangles in the macrocycle,
which are bridged by {Cr Ni-Py } rotaxane where the bis-pyridyl
8
(O
2
C Bu)16}]
3
[Fe
2
Co (μ
3
-
interaction, and there are recent proposals that weak hydrogen
bonds14 can become structure directing.
t
t
7
Ni-
2
2
a. School of Chemistry and Photon Science Institute, The University of Manchester,
Oxford Road, Manchester M13 9PL, UK.
7
2
b.
Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol),
Universidad de Valencia, 46980 Paterna, Valencia, Spain.
Chemistry Department, Sir David Davies Building, Loughborough University, LE11
7
2
c.
group lies close to the plane defined by the metal sites of the
triangle (Figure 2a). The final two rotaxanes bridge between the
3
TU, UK.
†Electronic Supplementary Information (ESI) available: Preparation and physical
characterization data of 1, 2 and 3 (Figures S1-S17). Crystallographic refinement
details for 1 and 3 (Table S1). CCDC-1572780 (1) and CCDC-1572781 (3). See
DOI: 10.1039/x0xx00000x
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Figure 1. Synthetic route leading to (a) the key component {Cr
7
Ni-Py
and [Ni
2 7
} 2 and (b) the doubly interlocked polymeric [c2]-daisy chain 3 (only the equatorial {Cr Ni} rings are shown for
the sake of clarity). Reaction conditions: (i) CrF
3
·4H
2
O
2
(μ-OH
2
)(O
2
CtBu)
Co(μ
4
(HO
-O)(O
2
CtBu)
4
], tBuCO
(H O) ], Me
2
H
(150 °C, 24 h); (ii) 3,5-bis(pyridin-4-ylethynyl)benzoic acid,
dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine, THF (r.t., 48 h, Ar) (iii) [Fe
2
3
2
CtBu)
6
2
3
2
CO (50 °C, 1h). The phenyl-stopper on the axle of the rotaxane is
represented as a gray sphere.
two pairs of triangles, perpendicular to the plane of the within the chain is therefore due to the widely spaced bis-
triangles, creating the hinge of the macrocycle. The macrocycle pyridine ligand at the terminus of the axle, and the {Cr
7
Ni} wheel
is sufficiently large that a [2]rotaxane from an adjacent has little to do with this primary structure.
macrocycle can pass through it, creating a doubly-interlocked There is one further complexity. Adjacent double-chains
structure; this is one of the two rotaxanes that does not form interpenetrate in the lattice through the second [2]rotaxane
the hinge of the macrocycle. This is shown in Figure 2b (and in that does not form the hinge. This is shown in Figure 2d, where
Figure S13), where one macrocycle is in red, and the adjacent we show four chains. The red and blue chains interpenetrate as
macrocycle is in blue.
shown in Figure 2c, but then singly interpenetrate with their
The macrocycles form [c2]-daisy chains growing along the neighbours; the light blue chain interacts with the red chain,
crystallographic a-axis (Figure 2c). Propagation occurs as each and the dark blue chain with the pink chain. This feature leads
metal triangle is part of two macrocycles. This could be to layers of interpenetrated polymeric [c2]-daisy chains in the
described as a (4,4) net, with each triangle acting as a four- ac plane that closely pack along the crystallographic c axis,
connected node, bound to two rotaxanes within a single without further interpenetration between the lateral [2]-
macrocycle. The rotaxanes that form the “hinge” of the rotaxanes from each pair of neutral interlocking double chains
macrocycle are therefore in two macrocycles. Propagation (Figure S15–S16).
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Figure 2. Perspective views of fragments of 3. (a) A single hinged macrocycle showing four triangles and four [2]rotaxanes. Co, orange; Cr, green; Ni, purple; Fe, brown; N, blue; O,
red; C, grey; F, pale green. (b) Two doubly interpenetrated macrocycles, one shown in blue the second in red. H atoms and the tert-butyl omitted for clarity. (c) Perspective view of
the interlocked double [c2]-daisy chain with H-atoms and butyl substitutents omitted for clarity. One chain is in red, the second in blue. (d) Interpenetration between neighbouring
double-chains, containing all C-atoms. Four chains are shown – two as in (c), the last two in light blue and pink.
This is an unusual polymeric daisy chain;8, 15, 18 there are related antiferromagnetic coupling within the {Cr
structures reported by Loeb and co-workers, which normally S17), and any inter-wheel exchange interactions are too small
7
Ni} rotaxanes (Figure
1
9
contain organic wheels as part of the structure. {Cr7Ni} wheels to be observed. EPR spectroscopy can be more informative in
2
2
have been studied as qubits for quantum information this context. X-band EPR spectra recorded on microcrystalline
2
0
processing (QIP), including recent proposals to perform two- samples of 3 (Figure S18) show the characteristic signals of
2
1
qubit quantum logic gates on assemblies. To move toward magnetically isolated {Fe
2
Co} triangles and {Cr
7
Ni} wheels and
Co}
Ni} wheels, without including any exchange
algorithms. With this in mind, we have studied the magnetic interaction between them. This puts an upper limit on the value
scalable devices, a very large number of interacting units and can be simulated using the known g-values for the {Fe
quantum gates would need to be assembled to perform useful triangles and {Cr
2
2
3
7
-1
and EPR spectroscopy of 3. The temperature dependence of the of the interaction of around 0.01 cm . Attempts to obtain
magnetic susceptibility of 3 is dominated by the strong pulsed EPR spectra failed as the echo-signal in 3 relaxes too fast
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Journal Name
1
2 J. Ferrando-Soria, A. Fernandez, E. Moreno PViienweAdrtaic,le SO.nliAne.
Varey, R. W. Adams, I. J. Vitorica-Yr
Timco, C. A. Muryn and R. E. P. Winpenny, J. Am. Chem. Soc.,
015, 137, 7644.
3 G. F. S. Whitehead, S. J. Teat, K. J. Gagnon, G. A. Timco and R.
E. P. Winpenny, Chem. Commun., 2015, 51, 3533.
to be detected. This is a common outcome in magnetically
concentrated samples. Attempts to produce magnetically
dilute versions of 3 are continuing.
Here we have reported an unusual interlocked structure, built
from two distinct polymetallic components. Further studies of
the use of 2 as a supramolecular building block are continuing.
2
4
ezaI:bal, F. Tuna, G. A.
DO 10.1039/C8CC09339C
2
1
1
4 (a) X. Yan, S. Li, J. B. Pollock, T. R. Cook, J. Chen, Y. Zhang, X.
Ji, Y. Yu, F. Huang and P. J. Stang, Proc. Natl. Acad. Sci. USA,
2
013, 110, 15585; (b) P. Wei, X. Yan and F. Huang, Chem. Soc.
Rev., 2015, 44, 815; (c) Z. Zhou, X. Yan, T. R. Cook, M. L. Saha
and P. J. Stang, J. Am. Chem. Soc., 2016, 138, 806.
5 (a) L. Fang, M. Hmadeh, J. Wu, M. A. Olson, J. M. Spruell, A.
Trabolsi, Y.-W. Yang, M. Elhabiri, A.-M. Albrecht-Gary and J. F.
Stoddart, J. Am. Chem. Soc., 2009, 131, 7126; (b) K. Iwaso, Y.
Takashima and A. Harada, Nat. Chem., 2016, 8, 625.
6 G. Chaboussant, R. Basler, H.-U. Güdel, S. Ochsenbein, A.
Parkin, S. Parsons, G. Rajaraman, A. Sieber, A. A. Smith, G. A.
Timco and R. E. P. Winpenny, Dalton Trans., 2004, 2758.
7 K. O. Abdulwahab, M. A. Malik, P. O’Brien, G. A. Timco, F.
Tuna, C. A. Muryn, R. E. P. Winpenny, R. A. D. Pattrick, V. S.
Coker and E. Arenholz, Chem. Mater., 2014, 26, 999.
Conflicts of interest
There are no conflicts to declare.
1
Acknowledgements
1
1
This work was supported by the EPSRC(UK) (grant number
EP/L018470/1), the European Commission (Marie Curie Intra-
European Fellowship to J.F.S. (622659) and A.F. (300402)). We
also thank EPSRC (UK) for funding an X-ray diffractometer (grant
number EP/K039547/1). We thank Diamond Light Source for 18 (a) C. J. Bruns, M. Frasconi, J. Iehl, K. J. Hartlieb, S. T.
Schneebeli, C. Cheng, S. I. Stupp and J. F. Stoddart, J. Am.
access to synchrotron X-ray facilities. Thanks, are also extended
to the “Subprograma atracció de talent-contractes
postdoctorals de la Universitat de Valencia” (J. F.-S.). We thank
Chem. Soc., 2014, 136, 4714; (b) A. Goujon, G. Du, E. Moulin,
G. Fuks, M. Maaloum, E. Buhler and N. Giuseppone, Angew.
Chem. Int. Ed., 2016, 55, 703.
Raymundo Hernandez for help with characterisation of 19 (a) V. N. Vukotic and S. J. Loeb, Chem. Eur. J., 2010, 16, 13630;
materials.
(b) N. C. Frank, D. J. Mercer and S. J. Loeb, Chem. Eur. J., 2013,
9, 14076; (c) G. Gholami, K. Zhu, J. S. Ward, P. E. Kruger and
1
S. J. Loeb, Eur. J. Inorg. Chem., 2016, 4524; (d) G. Gholami,
G.Baggi, K. Zhu and S. J. Loeb, Dalton Trans., 2017, 46, 2462.
0 C. J. Wedge, G. A. Timco, E. T. Spielberg, R. E. George, F. Tuna,
S. Rigby, E. J. L. McInnes, R. E. P. Winpenny, S. J. Blundell and
A. Ardavan, Phys. Rev. Lett., 2012, 108, 107204.
2
2
Notes and references
1
2
3
J.-M. Lehn, Supramolecular Chemistry: Concepts and
Perspectives (Wiley-VCH, Weinheim, 1995).
1 (a) A. Fernandez, J. Ferrando-Soria, E. Moreno Pineda, F. Tuna,
I. J. Vitorica-Yrezabal, C. Knappke, J. Ujma, C. A. Muryn, G. A.
Timco, P. E. Barran, A. Ardavan and R. E. P. Winpenny, Nat.
Commun., 2016, 7, 10240; (b) J. Ferrando-Soria, E. Moreno
Pineda, A. Chiesa, A. Fernandez, S. A. Magee, S. Carretta, P.
Santini, I. J. Vitorica-Yrezabal, F. Tuna, G. A. Timco, E. J. L.
McInnes and R. E. P. Winpenny, Nat. Commun., 2016, 7,
R. Chakrabarty, P. S. Mukherjee and P. J. Stang, Chem. Rev.,
2
011, 111, 6810.
(a) J.-P. Sauvage and C. Dietrich-Buchecker, Eds. Catenanes,
Rotaxanes, and Knots (Wiley-VCH, Weinheim, 1999); (b) J. F.
Stoddart, Chem. Soc. Rev., 2009, 38, 1802.
4
5
G. Gil-Ramírez, D. A. Leigh and A. J. Stephens, Angew. Chem.
Int. Ed., 2015, 54, 6110.
1
1377.
2
2
2 A. Fernandez, E. Moreno Pineda, C. A. Muryn, S. Sproules, F.
Moro, G. A. Timco, E. J. L. McInnes and R. E. P. Winpenny,
Angew. Chem. Int. Ed., 2015, 54, 10858.
R. McGonigal, P. Deria, I. Hod, P. Z. Moghadam, A.-J. Avestro,
N. E. Horwitz, I. C. Gibbs-Hall, A. K. Blackburn, D. Chen, Y. Y.
Botros, W. R. Wasielewski, R. Q. Snurr, J. T. Hupp, O. K. Farha
and J. F. Stoddart, Proc. Natl. Acad. Sci. USA, 2015, 112, 11161.
J.-F. Ayme, J. E. Beves, C. J. Campbell and D. A. Leigh, Chem.
Soc. Rev., 2013, 42, 1700.
3 J. Ferrando-Soria, S. A. Magee, A. Chiesa, S. Carretta, P.
Santini, I. J. Vitorica-Yrezabal, F. Tuna, G. F. S. Whitehead, S.
Sproules, K. M. Lancaster, A.-L. Barra, G. A. Timco, E. J. L.
McInnes and R. E. P Winpenny, Chem, 2016, 1, 727.
4 (a) M. Atzori, L. Tesi, E. Morra, M. Chiesa, L. Sorace and R.
Sessoli, J. Am. Chem. Soc., 2016, 138, 2154; (b) M. Shiddiq, D.
Komijani, Y. Duan, A. Gaita-Ariño, E. Coronado and S. Hill,
Nature, 2016, 531, 348.
6
7
(a) H. X. Deng, M. A. Olson, J. F. Stoddart and O. M. Yaghi, Nat.
Chem., 2010, 2, 439; (b) H.- Y. Gong, B. M. Rambo, W. Cho, V.
M. Lynch, M. Oh and J. L. Sessler, Chem. Commun. 2011, 47,
2
5
973; (c) V. N. Vukotic, K. J. Harris, K. Zhu, R. W. Schurko and
S. J. Loeb, Nat. Chem., 2012, 4, 456; (d) K. L. Zhu, C. A. O’Keefe,
V. N. Vukotic, R. W. Schurko and S. J. Loeb, Nat. Chem., 2015,
7
, 514.
M. Xue, Y. Yang, X. Chi, X. Yan and F. Huang, Chem. Rev., 2015,
15, 7398.
8
9
1
1
E. J. L. McInnes, G. A. Timco, G. F. S. Whitehead and R. E. P.
Winpenny, Angew. Chem. Int. Ed., 2015, 54, 14244.
0 (a) C.-F. Lee, D. A. Leigh, R. G. Pritchard, D. Schultz, S. J. Teat,
G. A. Timco and R. E. P. Winpenny, Nature, 2009, 458, 314; (b)
B. Ballesteros, T. B. Faust, C.-F. Lee, D. A. Leigh, C. A. Muryn,
R. G. Pritchard, D. Schultz, S. J. Teat, G. A. Timco and R. E. P.
Winpenny, J. Am. Chem. Soc., 2010, 132, 15435.
1 A. Fernandez, E. Moreno Pineda, J. Ferrando-Soria, E. J. L.
McInnes, G. A. Timco and R. E. P. Winpenny, Chem. Commun.,
2
1
015, 51, 11126.
4
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DOI: 10.1039/C8CC09339C
Formation of an Interlocked Double-Chain from an Organic-Inorganic [2]Rotaxane
Jesús Ferrando-Soria, Antonio Fernandez, Iñigo J. Vitorica-Yrezabal, Christopher A. Muryn,
Floriana Tuna, Grigore A. Timco and Richard E. P. Winpenny