Simultaneous Generation of a [2 × 2] Grid-Like Complex and a Linear Double Helicate: a Three-Level Self-Sorting Process

Article abstract of DOI:10.1021/jacs.0c00896

Two constitutional dynamic libraries (CDLs) - each containing two amines, two dialdehydes, and two metal salts - have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures (sharing no component) each with a [2 ×

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Simultaneous Generation of a [2 × 2] Grid-Like Complex and a
Linear Double Helicate: a Three-Level Self-Sorting Process
Jean-Franco̧ is Ayme, Jean-Marie Lehn,* Corinne Bailly, and Lydia Karmazin
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ABSTRACT: Two constitutional dynamic libraries (CDLs)each containing two amines, two
dialdehydes, and two metal saltshave been found to self-sort, generating two pairs of imine-
based metallosupramolecular architectures (sharing no component) each with a [2 × 2] grid-like
complex and a linear double helicate. These CDLs provided unique examples of a three-level self-
sorting process, as only two imine-based ligand constituents, two metal complexes, and two
architectures were selected during their assembly out of all the possible combinations of their
initial components. The metallosupramolecular architectures assembled were characterized by
NMR, mass spectroscopy, and X-ray crystallography.
and a linear double helicate, via the self-sorting of their initial
six different building blocks. The study provides a unique
example of a three-level self-sorting process: (i) at the
molecular level, only two specific imine based ligands were
formed via the self-sorting of the initial four different amine
and aldehyde components; (ii) at the supramolecular level,
only two specific metal complexes were generated via the self-
sorting of the imine-based ligands around the two types of
metal cations used; (iii) finally, only two specific architectures
were produced via the self-sorting of the assembled metal
complexes.
INTRODUCTION
■
By addressing both molecular and supramolecular levels,
constitutional dynamic chemistry (CDC) has provided
chemists with a powerful tool for controlling the organization
of chemical systems,1−3 in particular through the operation of
orthogonal self-assembly4 and self-sorting.5−9 Illustrative
examples of the organizational power of constitutional dynamic
systems at both levels can be found in architectures assembled
via the condensation of amine and 2-formylpyridine
components into dynamic imine-based ligand constituents
around transition metal cations.3a,b,9f−h,10,11
The concurrent assembly of several of these architectures
within the same reaction mixture was shown to promote the
emergence of new properties going beyond those of each
individual architecture, highlighting the importance of
fostering compositional diversity within constitutional dynamic
systems in order to extend the scope of their accessible
properties.1c,3b,8a,9f−h,11a−d,h However, to our knowledge,
literature reports only describe the self-assembly of constitu-
tional dynamic architectures having at least one component in
common (i.e., organic components and/or type of metal
cations).5,8,9 To increase the compositional diversity of the
manifold of assembled architectures, strategies are required
that allow the simultaneous control of the outcome of two (or
more) interconnected dynamic processes. Such a strategy is
offered, namely, by combining imine-based dynamic ligands
and by dynamic metal−ligand coordination bond formation.
In the present report, we describe two constitutional
dynamic libraries each enabling the concomitant generation
of a pair of imine-based metallosupramolecular architectures
(sharing no component) each with a [2 × 2] grid-like complex
RESULTS AND DISCUSSION
■
1. In the first study, we envisaged that the ligand selectivity
of Fe(II) cations should drive the evolution of a mixture
of components 1, 2, 3, and 4 toward the exclusive
formation of the linear double helicate [Fe2(3,42)2]4+
and the [2 × 2] grid-like complex [Cu4(1,22)4]4+ upon
addition of Fe(II) and Cu(I) salts (Scheme 1 and Figure
1), the notation (n,m2) refers to the imine-based
constituent generated by the condensation of aldehyde
n with two amines m. On the basis of previous work
from our group12 and on the preferred octahedral
coordination geometry of Fe(II), it was expected that
Received: January 23, 2020
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© XXXX American Chemical Society
A

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Scheme 1. Structures of Constituents (1,22) and (3,42)
Generated by Metallo-Selection during the Self-Sorting of
Components 1, 2, 3, and 4 in the Presence of Cu(I) and
Fe(II) Salts
Scheme 2. Structures of Constituents (5,42) and (7,62)
Generated by Metallo-Selection during the Self-Sorting of
Components 4, 5, 6, and 7 in the Presence of Cu(I) and
Zn(II) Salts
Figure 2. Top: Synthesis of complexes [Cu2(7,62)2]2+ and
[Zn4(5,42)4]8+ through the self-sorting of their initial reactants.
Reaction conditions: 4:5:6:7:Cu(BF4):Zn(BF4)2 (2:1:2:1:1:1),
CD3CN/CDCl3 2:1, 60 °C, 18 h. Bottom: Partial 1H NMR spectrum
(400 MHz, CD3CN/CDCl3 2:1, 298 K) of the crude reaction mixture
after 18 h at 60 °C. The diagnostic signals of the complexes are color
coded, [Cu2(7,62)2]2+ in red and [Zn4(5,42)4]8+ in green.
Figure 1. Top: Synthesis of complexes [Cu4(1,22)4]4+ and
[Fe2(3,42)2]4+ through the self-sorting of their initial reactants.
Reaction conditions: 1:2:3:4:Cu(BF4):Fe(BF4)2 (1:2:1:2:1:1),
CD3CN/CDCl3 2:1, 60 °C, 18 h. Bottom: Partial 1H NMR spectrum
(400 MHz, CD3CN/CDCl3 2:1, 298 K) of the crude reaction mixture
after 18 h at 60 °C. The diagnostic signals of the complexes are color
coded, [Cu4(1,22)4]4+ in red and [Fe2(3,42)2]4+ in purple.
Zn(II) cations were shown to require more steric
information in their initial set of components to yield a
similar degree of self-sorting.12 Therefore, despite the
significant steric congestion provided by the C6H6
bridge of 7, the substituted 8-amino-2-methylquinoline
4 was preferred over a regular 8-aminoquinoline to avoid
any scrambling of the ligands between the two
architectures at equilibrium. The linearity and rigidity
of 5 and the coordination preferences of Zn(II) should
ensure that [Zn4(5,42)4]8+ adopts a [2 × 2] grid-like
architecture,15 while the C6H6 bridge of 7 should allow
the twisting of the dinuclear complex [Cu2(7,62)2]2+ into
the helical shape characteristic of a linear double helicate
architecture.13,14
Fe(II) would preferentially bind the least sterically
hindered NNN-tridentate ligand accessible from the
initial components, namely, the condensation product of
3 with two amines 4. Subsequent to the formation of
[Fe2(3,42)2]4+, Cu(I) would, by default, have to bind to
the moderately sterically hindered bidentate coordina-
tion site offered by the condensation product of 1 with
two amines 2. The suitable flexibility of the CH2CH2
bridge of 3 should ensure that [Fe2(3,42)2]4+ adopts a
linear double helicate architecture,13,14 while the rigidity
and linearity of bis-imine (1,22) and the preferred
tetrahedral coordination geometry of Cu(I) should
enforce a [2 × 2] grid-like architecture to the
[Cu4(1,22)4]4+ complex.15,16 Considering the limited
steric congestion of 1, the sterically more demanding 8-
amino-2-methylquinoline 4 was preferred over an
unsubstituted 8-aminoquinoline to prevent the incorpo-
ration of 1 into Fe(II) complexes at equilibrium and to
improve the efficiency of the self-sorting process.12
Before the self-sorting experiments were attempted, the four
complexes were prepared separately to confirm their
architectures. Each of them was obtained by mixing 1 equiv
of the corresponding bis-aldehyde with 2 equiv of the
appropriate amine and 1 equiv of the corresponding metal
salt in a 2:1 CD3CN/CDCl3 mixed solvent. The reaction
mixtures were analyzed by NMR spectroscopy and ESI-MS
after 18 h of heating at 60 °C. As expected for the formation of
a [2 × 2] grid-like architecture or a linear double helicate
2. In a second study, we envisaged that the role of the
octahedrally and tetrahedrally coordinated metal cations
could be reversed so that, upon the addition of Zn(II)
and Cu(I) salts to a mixture of components 4, 5, 6, and
7, Zn(II) cations would drive the exclusive formation of
the [2 × 2] grid-like complex [Zn4(5,42)4]8+ and, as a
corollary, of the linear double helicate [Cu2(7,62)2]2+
(Scheme 2 and Figure 2). In comparison to Fe(II),
1
architecture, in all four cases, the H NMR spectra of the
solutions revealed the formation of highly symmetrical
complexes, as all the protons of the ligands of each complex
experienced a single chemical and magnetic environment
B
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Figure 3. Single crystal X-ray structures of linear double helicates [Fe2(3,42)2](PF6)4 and [Cu2(7,62)2](ClO4)2 and of [2 × 2] grid-like complexes
[[Cu4(1,22)4]·C6H6](BPh4)4 and [Zn4(5,42)4](BF4)8. Solvent molecules and counterions have been omitted for clarity.
(Supporting Information, Section 2.2). ESI-MS allowed the
determination of the absolute stoichiometry of the metal-
losupramolecular architectures generated. In each case, m/z
fragments matching with the molecular weights of the expected
aldehyde and 2 equiv of each monoamine in a 2:1 CD3CN/
CDCl3 mixed solvent. After 18 h of heating at 60 °C, the
outcome of both self-assembly processes was analyzed by
NMR spectroscopy. In the case of [Cu4(1,22)4]4+ and
[Fe2(3,42)2]4+(Supporting Information, Figures S30 and
−
architectures and the loss of BF4 anions during the ionization
1
S31), the H NMR spectra of the crude reaction mixture
process were obtained (Supporting Information, Section 2.2).
The analysis of the isotope pattern of these fragments
corroborated the formation of the desired complexes. In
some cases, additional proof of the nature of the architecture
was dominated by the diagnostic signals of the two expected
architectures, but some undefined side products were also
visible (Figure 1). The limited fidelity of this self-sorting
process, especially when compared to the simultaneous
generation of related mononuclear complexes,12 might reflect
the need for greater assembly instructions in the initial
components to compensate for the increased intricacy of the
assembly of polynuclear architectures. In the case of
[Cu2(7,62)2]2+ and [Zn4(5,42)4]8+ (Supporting Information,
1
could be obtained. In H NMR spectroscopy, the N−CH2
protons of [Cu4(1,22)4]4+ and the CH2 protons of the bridges
of [Fe2(3,42)2]4+ appeared as AB systems (J = 12.8 Hz and J =
11 Hz, respectively). Such AB patterns are characteristic of
methylene groups in asymmetric environments, such as the
one conferred by the rigid architectures of [2 × 2] grids or
linear double helicates.
1
Figures S32 and S33), the H NMR spectrum of the crude
reaction mixture revealed the exclusive conversion of the
starting materials into a clean mixture of the two metal-
losupramolecular architectures (Figure 2). The stronger
assembly instructions, engraved initially in the components
of the system to offset the less defined coordination
preferences of Zn(II) compared to Fe(II), were also sufficient
to impose the selective assembly of only these two
architectures. In both systems, the addition of only one of
the two metal cations to the initial library of components did
not yield a single complex, exemplifying how the simultaneous
assembly of two complexes can operate in synergy and how the
higher complexity of a system (i.e., a larger number of
components) may result in a simpler output, i.e., “simplexity”,
as was noted in previous instances.3b
X-ray-quality crystals of all four architectures were grown by
liquid−liquid diffusion (Supporting Information, Section 4). In
all cases, subsequent X-ray crystallographic studies established
the formation of the desired architecture (Figure 3). The two
metal ions of [Fe2(3,42)2](PF6)4 and [Cu2(7,62)2](ClO4)2 are
held adjacent by two ligand strands wrapped around each other
in a helical fashion. The coordination geometries around both
Fe(II) and Cu(I) are distorted octahedra and distorted
tetrahedra, respectively. The Cu(I) helicate is more compact
than the Fe(II) helicate (Cu,Cu distance is 4.8931(5) Å and
Fe,Fe distance is 8.877(2) Å). The metal ions of both
[[Cu4(1,22)4]·C6H6](BPh4)4 and [Zn4(5,42)4](BF4)8 lie al-
most in a plane (mean deviation of 0.3665(4) Å and 0.1830
(8) Å, respectively) and form a parallelogram (angles of 79.83
99.17°) and a square (angles of 89.94°), respectively. They
display distorted tetrahedral and distorted octahedral coordi-
nation of their metal centers to two perpendicularly oriented
ligands, respectively. A molecule of benzene lies in the central
cavity of the Cu(I) complex (average Cu,Cu distance is
7.913(7) Å) whereas, in the case of the Zn(II) complex, the
central cavity is occupied by disordered solvent molecules
(average Zn,Zn distance is 11.462(0) Å).
CONCLUSIONS
■
In the present investigations, we demonstrated that the
coordination preferences of tetrahedral and octahedral metal
ions can be exploited by ligand design to drive the
simultaneous and selective formation of two constitutionally
unrelated imine-based metallosupramolecular architectures
from their initial reactants. This self-assembly amounts to a
three-tier self-sorting process where the organization of the
system is controlled at both molecular and supramolecular
levels though the correct selection of only two imine-based
ligand constituents, two metal complexes, and two architec-
tures from the extended dynamic library of entities potentially
accessible via reversible interconnection of the initial reactants.
Having shown that all four architectures could be assembled
individually, we investigated the formation of [Cu4(1,22)4]4+
and [Fe2(3,42)2]4+ on one hand and of [Cu2(7,62)2]2+ and
[Zn4(5,42)4]8+ on the other hand from mixtures of their initial
building blocks. For these two reactions, 1 equiv of each of the
metal BF4− salts was added to a mixture of 1 equiv of each bis-
C
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The present study illustrates the delicate interplay of
coordination and structural/conformational features that
make up the information characteristics presented by the
components and are required for directing the final output of a
complex instructed mixture.
Learning how to concurrently control the outcome of
multiple dynamic processes shared by several entities within
the same reaction mixture is an important step toward
increased compositional diversity in constitutional dynamic
systems and, ultimately, self-assembling processes that rival
biological systems in complexity.
ACKNOWLEDGMENTS
■
J.F.A. gratefully acknowledges Prof. Jack Harrowfield, Dr. Jean-
Louis Schmitt, and Cyril Antheaume for extensive discussions.
ABBREVIATIONS
■
CDL, constitutional dynamic library; CDC, constitutional
dynamic chemistry; NMR, nuclear magnetic resonance; ESI-
MS, electrospray ionization mass spectrometry
REFERENCES
■
(1) For selected resources on the self-organization of chemical
systems: (a) Lehn, J.-M. Perspectives in ChemistrySteps towards
Complex Matter. Angew. Chem., Int. Ed. 2013, 52, 2836−2850.
(b) Ashkenasy, G.; Hermans, T. M.; Otto, S.; Taylor, A. F. Systems
Chemistry. Chem. Soc. Rev. 2017, 46, 2543−2554. (c) Ayme, J.-F.;
Lehn, J.-M. From Coordination Chemistry to Adaptive Chemistry.
Adv. Inorg. Chem. 2018, 71, 3−78.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c00896.
■
sı
Experimental procedures, spectral data for all com-
pounds, and details of the X-ray analyses (PDF)
Crystallographic data for ([Cu2(7,62)2](ClO4)2·xSol-
vent) (CIF)
Crystallographic data for ([Fe2(3,42)4](PF6)4·xSolvent)
(CIF)
Crystallographic data for ([[Cu4(1,22)4]·C6H6](BPh4)4·
xSolvent) (CIF)
(2) Constitutional Dynamic Chemistry; Barboiu, M., Ed.; Topics in
Current Chemistry; Springer: Berlin, 2012; Vol. 322.
(3) For selected recent examples of applications of Constitutional
Dynamic Chemistry: (a) Holub, J.; Vantomme, G.; Lehn, J.-M.
Training a Constitutional Dynamic Network for Effector Recognition:
Storage, Recall, and Erasing of Information. J. Am. Chem. Soc. 2016,
138, 11783−11791. (b) Men, G.; Lehn, J.-M. Higher Order
Constitutional Dynamic Networks: [2 × 3] and [3 × 3] Networks
Displaying Multiple, Synergistic and Competitive Hierarchical
Crystallographic data for ([Zn4(5,42)4](BF4)8·xSolvent)
(CIF)
̈
Adaptation. J. Am. Chem. Soc. 2017, 139, 2474−2483. (c) Low, H.;
Mena-Osteritz, E.; von Delius, M. Self-Assembled Orthoester
Cryptands: Orthoester Scope, Post-Functionalization, Kinetic Locking
and Tunable Degradation Kinetics. Chem. Sci. 2018, 9, 4785−4793.
(d) Osypenko, A.; Lehn, J.-M. Pattern Generation and Information
Transfer through a Liquid/Liquid Interface in 3D Constitutional
Dynamic Networks of Imine Ligands in Response to Metal Cation
Effectors. J. Am. Chem. Soc. 2019, 141, 12724−12737. (e) He, M.;
Lehn, J.-M. Time-Dependent Switching of Constitutional Dynamic
Libraries and Networks from Kinetic to Thermodynamic Distribu-
tions. J. Am. Chem. Soc. 2019, 141, 18560−18569.
AUTHOR INFORMATION
Corresponding Author
Jean-Marie Lehn − Institute of Nanotechnology, Karlsruhe
Institute of Technology, 76344 Eggenstein-Leopoldshafen,
■
́
Germany; Laboratoire de Chimie Supramoleculaire, Institut de
́
́
́
Science et d’Ingenierie Supramoleculaires, Universite de
Strasbourg, 67000 Strasbourg, France; orcid.org/0000-
0001-8981-4593; Email: lehn@unistra.fr
(4) For selected general resources on orthogonal self-assembly:
(a) Saha, M. L.; De, S.; Pramanik, S.; Schmittel, M. Orthogonality in
Discrete Self-Assembly − Survey of Current Concepts. Chem. Soc. Rev.
2013, 42, 6860−6909. (b) Wilson, A.; Gasparini, G.; Matile, S.
Functional Systems with Orthogonal Dynamic Covalent Bonds.
Chem. Soc. Rev. 2014, 43, 1948−1962. (c) Wei, P.; Yan, X.; Huang, F.
Supramolecular Polymers Constructed by Orthogonal Self-Assembly
Based on Host−Guest and Metal−Ligand Interactions. Chem. Soc.
Rev. 2015, 44, 815−832.
Authors
Jean-Franco
Institute of Technology, 76344 Eggenstein-Leopoldshafen,
̧
is Ayme − Institute of Nanotechnology, Karlsruhe
́
Germany; Laboratoire de Chimie Supramoleculaire, Institut de
́
́
́
Science et d’Ingenierie Supramoleculaires, Universite de
Strasbourg, 67000 Strasbourg, France
́
́
Corinne Bailly − Service de Radiocristallographie, Federation de
́
chimie Le Bel FR2010, Universite de Strasbourg, 67008
(5) For selected general resources on self-sorting: (a) Kramer, R.;
Lehn, J.-M.; Marquis-Rigault, A. Self-Recognition in Helicate Self-
Assembly: Spontaneous Formation of Helical Metal Complexes from
Mixtures of Ligands and Metal Ions. Proc. Natl. Acad. Sci. U. S. A.
1993, 90, 5394−5398. (b) Rowan, S. J.; Hamilton, D. G.; Brady, P.
A.; Sanders, J. K. M. Automated Recognition, Sorting, and Covalent
Self-Assembly by Predisposed Building Blocks in a Mixture. J. Am.
Chem. Soc. 1997, 119, 2578−2579. (c) Wu, A.; Isaacs, L. Self-Sorting:
The Exception or the Rule? J. Am. Chem. Soc. 2003, 125, 4831−4835.
Strasbourg, France
́
́
Lydia Karmazin − Service de Radiocristallographie, Federation
́
de chimie Le Bel FR2010, Universite de Strasbourg, 67008
Strasbourg, France
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.0c00896
Funding
́
(d) Safont-Sempere, M. M.; Fernandez, G.; Wurthner, F. Self-Sorting
̈
The authors acknowledge the financial support by the ERC
(Advanced Research Grant SUPRADAPT 290585) and the
University of Strasbourg Institute for Advanced Study
(USIAS). J.F.A. acknowledges the financial support by the
European Union’s Horizon 2020 research and innovation
program under the Marie Skłodowska-Curie grant agreement
No. 749351.
Phenomena in Complex Supramolecular Systems. Chem. Rev. 2011,
111, 5784−5814. (e) He, Z.; Jiang, W.; Schalley, C. A. Integrative
Self-Sorting: a Versatile Strategy for the Construction of Complex
Supramolecular Architecture. Chem. Soc. Rev. 2015, 44, 779−789.
(f) Hsu, C.-W.; Miljanic, O. S. Dynamic Covalent Chemistry: Principles,
Reactions, and Applications, Zhang, W.; Jin, Y., Eds., John Wiley &
Sons Ltd:: Chichester, UK, 2017; pp 253−284;. (g) Schmittel, M.;
Saha, S. From Self-Sorting of Dynamic Metal-Ligand Motifs to
(Supra)molecular Machinery in Action. Adv. Inorg. Chem. 2018, 71,
135−176.
̌
́
Notes
The authors declare no competing financial interest.
D
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Article
(6) For selected examples of self-sorting processes based on dynamic
̈
̈
covalent bonds: (a) Icļ i, B.; Christinat, N.; Tonnemann, J.; Schuttler,
C.; Scopelliti, R.; Severin, K. Synthesis of Molecular Nanostructures
Structures Self-Assemble in the Cavities of Cuboctahedral Coordina-
tion Cages. J. Am. Chem. Soc. 2018, 140, 11502−11509.
(10) For selected examples of the diversity of metallo-supra-
molecular architectures reachable from amine-and 2-formylpyridine-
containing components: (a) Chichak, K. S.; Cantrill, S. J.; Pease, A.
R.; Chiu, S.-H.; Cave, G. W. V.; Atwood, J. L.; Stoddart, J. F.
Molecular Borromean Rings. Science 2004, 304, 1308−1312.
(b) Nitschke, J. R. Construction, Substitution, and Sorting of
Metallo-organic Structures via Subcomponent Self-Assembly. Acc.
Chem. Res. 2007, 40, 103−112. (c) Ayme, J.-F.; Beves, J. E.; Leigh, D.
A.; McBurney, R. T.; Rissanen, K.; Schultz, D. A Synthetic Molecular
Pentafoil Knot. Nat. Chem. 2012, 4, 15−20. (d) Beves, J. E.;
Campbell, C. J.; Leigh, D. A.; Pritchard, R. G. Tetrameric Cyclic
Double Helicates as a Scaffold for a Molecular Solomon Link. Angew.
Chem., Int. Ed. 2013, 52, 6464−6467. (e) Wood, C. S.; Ronson, T. K.;
Belenguer, A. M.; Holstein, J. J.; Nitschke, J. R. Two-Stage Directed
Self-Assembly of a Cyclic [3]catenane. Nat. Chem. 2015, 7, 354−358.
(11) For selected examples of the functional potential of
metallosupramolecular architecture built from amine-and 2-formyl-
pyridine-containing components: Potential for adaptation to stimuli,
see ref 2. and (a) Campbell, V. E.; de Hatten, X.; Delsuc, N.;
Kauffmann, B.; Huc, I.; Nitschke, J. R. Cascading Transformations
within a Dynamic Self-Assembled System. Nat. Chem. 2010, 2, 684−
687. (b) McConnell, A. J.; Wood, C. S.; Neelakandan, P. P.; Nitschke,
J. R. Stimuli-Responsive Metal−Ligand Assemblies. Chem. Rev. 2015,
115, 7729−7793. (c) Roberts, D. A.; Pilgrim, B. S.; Nitschke, J. R.
Covalent Post-Assembly Modification in Metallosupramolecular
Chemistry. Chem. Soc. Rev. 2018, 47, 626−644. (d) Roberts, D. A.;
Pilgrim, B. S.; Sirvinskaite, G.; Ronson, T. K.; Nitschke, J. R. Covalent
Post-assembly Modification Triggers Multiple Structural Trans-
formations of a Tetrazine-Edged Fe4L6 Tetrahedron. J. Am. Chem.
Soc. 2018, 140, 9616−9623. (e) Pramanik, S.; Aprahamian, I.
Hydrazone Switch-Based Negative Feedback Loop. J. Am. Chem.
Soc. 2016, 138, 15142−15145. Potential as molecular container
(f) Zarra, S.; Wood, D. M.; Roberts, D. A.; Nitschke, J. R. Molecular
Containers in Complex Chemical Systems. Chem. Soc. Rev. 2015, 44,
419−432. Potential as biologically active molecules or as mimic of
biological molecules (g) Kaner, R.; Allison, S.; Faulkner, A.; Phillips, R.;
Roper, D.; Shepherd, S.; Simpson, D.; Waterfield, N.; Scott, P.
Anticancer Metallohelices: Nanomolar Potency and High Selectivity.
Chem. Sci. 2016, 7, 951−958. Potential in polymeric materials
(h) Chow, C.-F.; Fujii, S.; Lehn, J.-M. Metallodynamers: Neutral
Double-Dynamic Metallosupramolecular Polymers. Chem. - Asian J.
2008, 3, 1324−1335. (i) Ulrich, S.; Lehn, J.-M. Reversible Switching
between Macrocyclic and Polymeric States by Morphological Control
in a Constitutional Dynamic System. Angew. Chem., Int. Ed. 2008, 47,
2240−2243. Potential as anion binder (j) Ayme, J.-F.; Beves, J. E.;
Campbell, C. J.; Gil-Ramírez, G.; Leigh, D. A.; Stephens, A. J. Strong
and Selective Anion Binding within the Central Cavity of Molecular
Knots and Links. J. Am. Chem. Soc. 2015, 137, 9812−9815.
(k) Bilbeisi, R. A.; Prakasam, T.; Lusi, M.; El-Khoury, R.; Platas-
by Multicomponent Condensation Reactions in a Ball Mill. J. Am.
̌
́
Chem. Soc. 2009, 131, 3154−3155. (b) Hsu, C. W.; Miljanic, O. S.
Adsorption-Driven Self-Sorting of Dynamic Imine Libraries. Angew.
Chem., Int. Ed. 2015, 54, 2219−2222. (c) Klotzbach, S.; Beuerle, F.
Shape-Controlled Synthesis and Self-Sorting of Covalent Organic
Cage Compounds. Angew. Chem., Int. Ed. 2015, 54, 10356−10360.
(7) For selected examples of self-sorting processes based on metal
complexes: (a) Zheng, Y. R.; Yang, H. B.; Ghosh, K.; Zhao, L.; Stang,
P. J. Multicomponent Supramolecular Systems: Self-Organization in
Coordination-Driven Self-Assembly. Chem. - Eur. J. 2009, 15, 7203−
7214. (b) Johnson, A. M.; Hooley, R. J. Steric Effects Control Self-
Sorting in Self-Assembled Clusters. Inorg. Chem. 2011, 50, 4671−
4673. (c) Lu, X.; Li, X.; Guo, K.; Xie, T.-Z.; Moorefield, C. N.;
Wesdemiotis, C.; Newkome, G. R. Probing a Hidden World of
Molecular Self-Assembly: Concentration-Dependent, Three-Dimen-
sional Supramolecular Interconversions. J. Am. Chem. Soc. 2014, 136,
18149−18155. (d) Bloch, W. M.; Holstein, J. J.; Hiller, W.; Clever, G.
H. Morphological Control of Heteroleptic cis- and trans-Pd2L2L′2
Cages. Angew. Chem., Int. Ed. 2017, 56, 8285−8289.
(8) For selected examples of self-sorting processes based on
́
constitutional dynamic metal complexes: (a) Jimenez, A.; Bilbeisi,
R. A.; Ronson, T. K.; Zarra, S.; Woodhead, C.; Nitschke, J. R.
Selective Encapsulation and Sequential Release of Guests Within a
Self-Sorting Mixture of Three Tetrahedral Cages. Angew. Chem., Int.
Ed. 2014, 53, 4556−4560. (b) Ayme, J.-F.; Beves, J. E.; Campbell, C.
J.; Leigh, D. A. The Self-Sorting Behavior of Circular Helicates and
Molecular Knots and Links. Angew. Chem., Int. Ed. 2014, 53, 7823−
7827. (c) Holloway, L. R.; Young, M. C.; Beran, G. J.; Hooley, R. J.
High Fidelity Sorting of Remarkably Similar Components via Metal-
Mediated Assembly. Chem. Sci. 2015, 6, 4801−4806. (d) Johnson, A.
M.; Wiley, C. A.; Young, M. C.; Zhang, X.; Lyon, Y.; Julian, R. R.;
Hooley, R. J. Narcissistic Self-Sorting in Self-Assembled Cages of Rare
Earth Metals and Rigid Ligands. Angew. Chem., Int. Ed. 2015, 54,
5641−5645. (e) Wiley, C. A.; Holloway, L. R.; Miller, T. F.; Lyon, Y.;
Julian, R. R.; Hooley, R. J. Electronic Effects on Narcissistic Self-
Sorting in Multicomponent Self-Assembly of Fe-Iminopyridine meso-
Helicates. Inorg. Chem. 2016, 55, 9805−9815. (f) Holloway, L. R.;
Bogie, P. M.; Hooley, R. J. Controlled Self-Sorting in Self-Assembled
Cage Complexes. Dalton Trans. 2017, 46, 14719−14723.
(9) For selected examples on self-sorting processes involving
supramolecular architectures built around more than one type of
metal template: (a) Sun, X.; Johnson, D. W.; Caulder, D. L.; Powers,
R. E.; Raymond, K. N.; Wong, E. H. Exploiting Incommensurate
Symmetry Numbers: Rational Design and Assembly of M2M′3,
L6Supramolecular Clusters with C3h Symmetry. Angew. Chem., Int. Ed.
1999, 38, 1303−1307. (b) Ibukuro, F.; Fujita, M.; Yamagushi, K.;
Sauvage, J.-P. Quantitative and Spontaneous Formation of a Doubly
Interlocking [2]Catenane Using Copper(I) and Palladium(II) as
Templating and Assembling Centers. J. Am. Chem. Soc. 1999, 121,
11014−11015. (c) Wise, M. D.; Holstein, J. J.; Pattison, P.; Besnard,
C.; Solari, E.; Scopelliti, R.; Bricogne, G.; Severin, K. Large,
Heterometallic Coordination Cages Based on Ditopic Metallo-
Ligands with 3-Pyridyl Donor Groups. Chem. Sci. 2015, 6, 1004−
1010. (d) Sepehrpour, H.; Saha, M. L.; Stang, P. J. Fe−Pt Twisted
Heterometallic Bicyclic Supramolecules via Multicomponent Self-
Assembly. J. Am. Chem. Soc. 2017, 139, 2553−2556. (e) Gaikwad, S.;
Saha, M. L.; Samanta, D.; Schmittel, M. Five-Component Trigonal
Nanoprism with Six Dynamic Corners. Chem. Commun. 2017, 53,
8034−8037. (f) Saha, M. L.; Schmittel, M. From 3-Fold Completive
Self-Sorting of a Nine-Component Library to a Seven-Component
Scalene Quadrilateral. J. Am. Chem. Soc. 2013, 135, 17743−17746.
(g) Ramsay, W. J.; Szczypinski, F. T.; Weissman, H.; Ronson, T. K.;
Smulders, M. M. J.; Rybtchinski, B.; Nitschke, J. R. Designed
Enclosure Enables Guest Binding Within the 4200 Å3 Cavity of a Self-
Assembled Cube. Angew. Chem., Int. Ed. 2015, 54, 5636−5640.
(h) Rizzuto, F. J.; Ramsay, W. J.; Nitschke, J. R. Otherwise Unstable
̀
Iglesias, C.; Charbonniere, L. J.; Olsen, J.-C.; Elhabiri, M.; Trabolsi, A.
[C−H···Anion] Interactions Mediate the Templation and Anion
Binding Properties of Topologically Non-Trivial Metal−Organic
Structures in Aqueous Solutions. Chem. Sci. 2016, 7, 2524−2532.
(12) Ayme, J.-F.; Lehn, J.-M. Self-Sorting of Two Imine-Based Metal
Complexes: Balancing Kinetics and Thermodynamics in Constitu-
tional Dynamic Networks. Chem. Sci. 2020, 11, 1114−1121.
(13) For selected examples on metallo−supramolecular helicates:
(a) Constable, E. C. Comprehensive Supramolecular Chemistry;
̈
Atwood, J. L., Davies, J. E. D., Macnicol, D. D., Vogtle, F., Lehn, J.-
M., Eds.; Pergamon: Oxford, 1996; Vol. 9; pp 213−252;. (b) Piguet,
C.; Bernardinelli, G.; Hopfgartner, G. Helicates as Versatile
Supramolecular Complexes. Chem. Rev. 1997, 97, 2005−2062.
(c) Yashima, E.; Ousaka, N.; Taura, D.; Shimomura, K.; Ikai, T.;
Maeda, K. Supramolecular Helical Systems: Helical Assemblies of
Small Molecules, Foldamers, and Polymers with Chiral Amplification
and Their Functions. Chem. Rev. 2016, 116, 13752−13990.
E
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Journal of the American Chemical Society
pubs.acs.org/JACS
Article
(14) Rapenne, G.; Dietrich-Buchecker, C.; Sauvage, J.-P. Copper(I)-
or Iron(II)-Templated Synthesis of Molecular Knots Containing Two
Tetrahedral or Octahedral Coordination Sites. J. Am. Chem. Soc. 1999,
121, 994−1001.
(15) For selected examples on [2 × 2] grid-like complexes:
(a) Ruben, M.; Rojo, J.; Romero-Salguero, F. J.; Uppadine, L. H.;
Lehn, J.-M. Grid-Type Metal Ion Architectures: Functional Metal-
losupramolecular Arrays. Angew. Chem., Int. Ed. 2004, 43, 3644−3662.
(b) Dawe, L. N.; Shuvaev, K. V.; Thompson, L. K. Polytopic Ligand
Directed Self-AssemblyPolymetallic [n × n] Grids versus Non-Grid
Oligomers. Chem. Soc. Rev. 2009, 38, 2334−2359. (c) Hardy, J. G.
Metallosupramolecular Grid Complexes: towards Nanostructured
Materials with High-Tech Applications. Chem. Soc. Rev. 2013, 42,
7881−7899.
(16) Baxter, P. N. W.; Lehn, J.-M.; Kneisel, B. O.; Fenske, D. Self-
Assembly of a Symmetric Tetracopper Box-Grid with Guest Trapping
in the Solid State. Chem. Commun. 1997, 2231−2232.
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https://dx.doi.org/10.1021/jacs.0c00896
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