Self-organization by selection: Generation of a metallosupramolecular grid architecture by selection of components in a dynamic library of ligands

Nitschke, Jonathan R.; Lehn, Jean‐Maríe

doi:10.1073/pnas.1534925100

Cited by 136 publications

(67 citation statements)

References 41 publications

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“…Determination of T gel as a function of the concentration of 1 for different cations showed that K ϩ was the most efficient gelator͞G 4 assembler. The other cations showed the sequence of gelation efficiency Me 4 N ϩ Ͼ NH 4 ϩ Ͼ Na ϩ (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…It generates constitutional dynamic libraries (CDLs) whose constituents are in dynamic equilibrium, such that they can exchange their components and express all of the entities that are potentially accessible through recombination by means of reversible covalent bonds and noncovalent interactions. The CDL may then adapt to (internal or) external physical factors or chemical effectors by selection (3,4) of the appropriate components for the optimal constituent. Such processes form the basis of the recently developed dynamic combinatorial chemistry (5,6), in which molecular recognition events have been implemented toward the generation of optimal binding agents toward artificial or biological (7) molecular receptors through a target-driven shift in the distribution of the library constituents toward the best binder(s).…”

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confidence: 99%

“…It would represent a process of self-organization by selection (3,4) by which the formation of a structured phase drives the selection of the components that make up the dynamic constituent producing the most highly organized and most stable assembly. Gels attract much current interest for their potential as intriguing materials (10,11) and as substrates for biomedical applications (12,13).…”

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confidence: 99%

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Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation

Sreenivasachary

Lehn

2005

Proc. Natl. Acad. Sci. U.S.A.

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330

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The guanosine hydrazide 1 yields a stable supramolecular hydrogel based on the formation of a guanine quartet (G-quartet) in presence of metal cations. The effect of various parameters (concentration, nature of metal ion, and temperature) on the properties of this gel has been studied. Proton NMR spectroscopy is shown to allow a molecular characterization of the gelation process. Hydrazide 1 and its assemblies can be reversibly decorated by acylhydrazone formation with various aldehydes, resulting in formation of highly viscous dynamic hydrogels. When a mixture of aldehydes is used, the dynamic system selects the aldehyde that leads to the most stable gel. Mixing hydrazides 1, 9 and aldehydes 6, 8 in 1:1:1:1 ratio generated a constitutional dynamic library containing the four acylhydrazone derivatives A, B, C, and D. The library constitution displayed preferential formation of the acylhydrazone B that yields the strongest gel. Thus, gelation redirects the acylhydrazone distribution in the dynamic library as guanosine hydrazide 1 scavenges preferentially aldehyde 8, under the pressure of gelation because of the collective interactions in the assemblies of G-quartets B, despite the strong preference of the competing hydrazide 9 for 8. Gel formation and component selection are thermoreversible. The process amounts to gelation-driven selforganization with component selection and amplification in constitutional dynamic hydrogels based on G-quartet formation and reversible covalent connections. The observed self-organization and component selection occur by means of a multilevel selfassembly involving three dynamic processes, two of supramolecular and one of reversible covalent nature. They extend constitutional dynamic chemistry to phase-organization and phasetransition events.dynamic combinatorial chemistry ͉ component selection ͉ supramolecular chemistry S upramolecular entities present the ability to reversibly modify their constitution through exchange and rearrangement of their molecular components because of the lability of the noncovalent interactions that hold them together (1, 2). Similar features may be imported into molecular species if reversible covalent bonds are introduced into their structure, allowing cleavage and formation of interatomic connections with fragment exchange under specific conditions. Thus, entities, capable of reversible modification of their constitution, define a constitutional dynamic chemistry on both the supramolecular and the molecular levels (3). Because the constitutional changes may be expected to respond to external factors, constitutional dynamic chemistry is the basis for the design and development of adaptive chemical systems. It generates constitutional dynamic libraries (CDLs) whose constituents are in dynamic equilibrium, such that they can exchange their components and express all of the entities that are potentially accessible through recombination by means of reversible covalent bonds and noncovalent interactions. The CDL may then adapt to (internal or) external phy...

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation

Sreenivasachary

Lehn

2005

Proc. Natl. Acad. Sci. U.S.A.

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330

195

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“…Following the proposition that such self‐organization processes are equally responsible for the dynamic generation of molecular and supramolecular diversity and complexity in three‐dimensional (3D) bulk structures,12, 13, 14, 15 we herein report on the complexation of a homoditopic ligand with two tridentate chelates with iron(II) and the accompanying tautomerism‐driven emergence of complexity. Whereas a number of ligands with tridentate chelates and tautomeric subunits have previously been described,16, 17, 18, 19, 20 we are not aware of any examples that describe the presence of different tauto‐conformers and the parallel formation of isomeric reaction products.…”

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Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers

et al. 2016

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The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism‐driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [FeII 4 L 4]8+ complexes were determined by X‐ray diffraction, and the distinctness of the products was confirmed by ion‐mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (FeII spin crossover vs. a blocked FeII high‐spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology.

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“…This ''subcomponent self-assembly'' has its roots in the template synthesis of Busch and coworkers (16) and has recently been used in the synthesis of a wealth of structures, including rotaxanes (17), catenanes (18), helicates (19)(20)(21)(22), grids (23)(24)(25), and a Borromean link (26). These structures belong to the domains of both dynamic covalent (27) and supramolecular (28) chemistry and offer a particularly rich set of possibilities for dynamic rearrangement at both covalent and dative linkages (29).…”

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Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

Schultz

Nitschke

2005

Proc. Natl. Acad. Sci. U.S.A.

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The technique of subcomponent self-assembly has been applied to the preparation of a set of copper(I) complexes from diamines and aldehydes in aqueous solution. These complexes may be synthesized alongside one another in solution despite the chemical nonorthogonality of their respective starting materials; thermodynamic equilibration eliminates all mixed products. The reactivity of these complexes has been studied, revealing that in certain cases, the substitution of both ligands and ligand subcomponents could be independently carried out. In one particular case, a complex was shown to be inert to ligand substitution but readily underwent ligand subcomponent substitution, creating the possibility of a previously undocumented kind of cascade reaction: Once ligand subcomponent substitution had occurred, ligand exchange could then happen, allowing both reactions to be triggered by a single chemical event.self-assembly ͉ coordination chemistry ͉ cascade reactions T he generation of complex metal-containing architectures from simple building blocks through self-assembly (1-8) is a compelling means by which to build up functional molecular machines (9-11). Such molecular devices are beginning to give substance to the promises of nanotechnology; recent examples include Mirkin and coworkers' (12) signal-amplifying allosteric catalyst, Nolte and colleagues' (13) ''chain-walking'' epoxidation catalyst, Leigh and coworkers' (14) reversible molecular motor, and the molecular elevator of Stoddart and colleagues (15).A powerful technique in metallo-organic self-assembly consists of the simultaneous formation of covalent (carbonheteroatom) and dative (heteroatom-metal) bonds, bringing both ligand and complex into being at the same time. This ''subcomponent self-assembly'' has its roots in the template synthesis of Busch and coworkers (16) and has recently been used in the synthesis of a wealth of structures, including rotaxanes (17), catenanes (18), helicates (19-22), grids (23-25), and a Borromean link (26). These structures belong to the domains of both dynamic covalent (27) and supramolecular (28) Because subcomponent self-assembly reactions operate on two distinct levels simultaneously, one might expect that these reactions would give rise to mixtures of diverse products or large dynamic combinatorial libraries (30-35), as the multiple components combine in different ways. Although many structures might in theory be possible at both covalent and supramolecular levels, the metal and the subcomponents of the ligand may be chosen such that the thermodynamic preferences of both converge to give rise to a single product or a limited number of products (22)(23)(24)(36)(37)(38). It is important to note that it is the reversible formation of intraligand imine bonds (in addition to the metal-ligand bonds) that allows for this dynamic sorting͞ selection effect to occur.Along similar lines, although the addition of further ligand components might be expected to increase the number of species present in the product mixture, it is non...

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Self-organization by selection: Generation of a metallosupramolecular grid architecture by selection of components in a dynamic library of ligands

Cited by 136 publications

References 41 publications

Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation

Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation

Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers

Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

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