Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Chakrabarty, Rajesh; Mukherjee, Partha Sarathi; Stang, Peter J.

doi:10.1021/cr200077m

Cited by 2,662 publications

(1,602 citation statements)

References 857 publications

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“…The complexation of the free ligand, H6L 4 , with Zn 2+ afforded two kinds of complexes, L 4 Zn3 and L 4 Zn5, which unexpectedly showed opposite CD signals. When up to 3 equivalent.…”

Section: Helicity Inversion By Metal Exchangementioning

confidence: 99%

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Dynamic Helicity Control of Oligo(salamo)-Based Metal Helicates

Akine

2018

Inorganics

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Much attention has recently focused on helical structures that can change their helicity in response to external stimuli. The requirements for the invertible helical structures are a dynamic feature and well-defined structures. In this context, helical metal complexes with a labile coordination sphere have a great advantage. There are several types of dynamic helicity controls, including the responsive helicity inversion. In this review article, dynamic helical structures based on oligo(salamo) metal complexes are described as one of the possible designs. The introduction of chiral carboxylate ions into Zn 3 La tetranuclear structures as an additive is effective to control the P/M ratio of the helix. The dynamic helicity inversion can be achieved by chemical modification, such as protonation/deprotonation or desilylation with fluoride ion. When (S)-2-hydroxypropyl groups are introduced into the oligo(salamo) ligand, the helicity of the resultant complexes is sensitively influenced by the metal ions. The replacement of the metal ions based on the affinity trend resulted in a sequential multistep helicity inversion. Chiral salen derivatives are also effective to bias the helicity; by incorporating the gauche/anti transformation of a 1,2-disubstituted ethylene unit, a fully predictable helicity inversion system was achieved, in which the helicity can be controlled by the molecular lengths of the diammonium guests.

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“…The complexation of the free ligand, H6L 4 , with Zn 2+ afforded two kinds of complexes, L 4 Zn3 and L 4 Zn5, which unexpectedly showed opposite CD signals. When up to 3 equivalent.…”

Section: Helicity Inversion By Metal Exchangementioning

confidence: 99%

“…The representative examples are self-assembled coordination compounds, such as macrocycles, cages, giant spheres, etc. [3][4][5].…”

Section: Dynamic Helical Structuresmentioning

confidence: 99%

Dynamic Helicity Control of Oligo(salamo)-Based Metal Helicates

Akine

2018

Inorganics

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“…Yang and coworkers (8) reported hydrogen-bonded supramolecular polymers and studied their polymerization mechanisms and physical properties based on the photoisomerization of the stiff-stilbene units. Nevertheless, stiff-stilbene-based supramolecular entities are underexplored despite exhibiting properties that make the functionality potentially useful in the construction of photoresponsive supramolecular materials.Coordination-driven self-assembly is a powerful method of constructing supramolecular coordination complexes (SCCs) by the spontaneous formation of metal-ligand bonds that draws inspiration from the design principles of natural systems (9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). This approach organizes metal acceptors and organic donors to prepare well-defined cavity-cored 2D metallacycles and 3D metallacages, which can be functionalized on their interior or exterior vertices for applications in host-guest chemistry (21, 22), catalysis (23), molecular flasks (24), bioengineering (25), amphiphilic self-assembly (26), and so on.…”

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confidence: 99%

Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers

Yan

Jiang

Cook

et al. 2014

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

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130

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Control over structural transformations in supramolecular entities by external stimuli is critical for the development of adaptable and functional soft materials. Herein, we have designed and synthesized a dipyridyl donor containing a central Z-configured stiff-stilbene unit that self-assembles in the presence of two 180°di-Pt(II) acceptors to produce size-controllable discrete organoplatinum(II) metallacycles with high efficiency by means of the directionalbonding approach. These discrete metallacycles undergo transformation into extended metallosupramolecular polymers upon the conformational switching of the dipyridyl ligand from Z-configured (0°) to E-configured (180°) when photoirradiated. This transformation is accompanied by interesting morphological changes at nanoscopic length scales. The discrete metallacycles aggregate to spherical nanoparticles that evolve into long nanofibers upon polymer formation. These fibers can be reversibly converted to cyclic oligomers by changing the wavelength of irradiation, which reintroduces Z-configured building blocks owing to the reversible nature of stiff-stilbene photoisomerization. The design strategy defined here represents a novel self-assembly pathway to deliver advanced supramolecular assemblies by means of photocontrol.metal coordination | supramolecular coordination complex | photoirradiation | reversibility | dynamic materials N atural systems provide many examples of self-assembled biosupramolecules that respond to external stimuli through conformational changes that ultimately play a role in carrying out their various biological functions. Mimicking this stimuli-responsive behavior in artificial systems is a promising route toward obtaining sophisticated molecular-based architectures with functional and structural tunability (1-3). Using the absorption of photons as a trigger is particularly attractive in that light-induced transformations maintain high spatial and temporal resolution without producing waste products even during multiple reversible switching sequences (4). In materials science, one of the most appealing characteristics of photochromic molecules is the direct conversion of light into mechanical energy based on their photo-reversible structural transformations (5). Among such chromophores, a stiffstilbene moiety (1,1′-biindane) is useful owing to its unique characteristics (6). First, stiff stilbene can adopt either a cis or trans configuration with respect to its central double bond. Second, the high activation barrier between the two isomers (∼43 kcal·mol −1 , corresponding to a half-life of ∼10 9 y at 300 K) makes thermal E/Z isomerization negligible at temperatures of 420 K and lower. Third, the quantum yield for the photoisomerization of either isomer is high (50%). Fourth, the stiff-stilbene core is readily substituted using well-established synthetic methods. Owing to these promising characteristics, Boulatov and coworkers (7) constructed a molecular force probe by integrating the moiety into a stretched polymer to mimic the strain gen...

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“…By carefully combining selected building blocks, discrete supramolecular coordination complexes (SCCs) can be obtained (27)(28)(29)(30)(31), based on the number and orientation of the labile coordination sites (for metal acceptors) and Lewis basic moieties (for organic donors). Because these metal-ligand interactions are general for a wide number of transition metals and organic linkers, a sizable library of 2D and 3D structures spanning multiple synthetic approaches has been developed over the last two decades.…”

mentioning

confidence: 99%

“…Because these metal-ligand interactions are general for a wide number of transition metals and organic linkers, a sizable library of 2D and 3D structures spanning multiple synthetic approaches has been developed over the last two decades. These synthetic strategies are unified under the theme of directional bonding, which reduces a target architecture to its constituent edges, faces, and vertices and seeks to replicate these on a molecular level (27). The substantial body of synthetic research has paved the way for multifunctional applications of SCCs ranging from molecular topology (32)(33)(34) and catalysis (35,36) to light harvesting and gas capture (37,38).…”

mentioning

confidence: 99%

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Yan

Pollock

et al. 2013

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

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223

116

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A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal-ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science.

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Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Cited by 2,662 publications

References 857 publications

Dynamic Helicity Control of Oligo(salamo)-Based Metal Helicates

Dynamic Helicity Control of Oligo(salamo)-Based Metal Helicates

Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

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