Multi-stimuli Control over Assembly and Guest Binding in Metallo-supramolecular Hosts Based on Dithienylethene Photoswitches.
TLDR
In this paper, a system of interconverting bowls and cages that are able to respond to various selective stimuli (light, ligands, anions), based on the self-assembly of a photochromic dithienylethene (DTE) ligand, La, with PdII cations, was presented.Abstract:
It is difficult to assemble multi-component metallo-supramolecular architectures in a non-statistical fashion, which limits their development toward functional materials. Herein, we report a system of interconverting bowls and cages that are able to respond to various selective stimuli (light, ligands, anions), based on the self-assembly of a photochromic dithienylethene (DTE) ligand, La, with PdII cations. By combining the concept of "coordination sphere engineering", relying on bulky quinoline donors, with reversible photoswitching between the ligand's open (o-La) and closed (c-La) forms, a [Pd2(o-La)4] cage (o-C) and a [Pd2(c-La)3] bowl (c-B) were obtained, respectively. This structural rearrangement modulates the system's guest uptake capabilities. Among three bis-sulfonate guests (G1, G2, and G3), the cage can encapsulate only the smallest (G1), while the bowl binds all of them. Bowl c-B was further used to synthesize a series of heteroleptic cages, [Pd2LA3LB], representing a motif never reported before. Additional ligands (Lc-f), with short or long arms, tune the cavity size, thus enabling or preventing guest uptake. Addition of Br-/Ag+ makes it possible to change the overall charge, again triggering guest uptake and release, as well as fourth ligand de-/recomplexation. In combination, site-selective introduction of functionality and application of external stimuli lead to an intricate system of hosts with different guest preferences. A high degree of complexity is achieved through cooperativity between only a few components.read more
Citations
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Increasing structural and functional complexity in self-assembled coordination cages.
TL;DR: In this article, a review of the implementation of function into self-assembled cages and strategies to selectively form heteroleptic structures is presented, including multicomponent multifunctional host-guest complexes and their potential in application in areas such as sensing, catalysis, and photo-redox systems.
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Beyond Platonic: How to Build Metal–Organic Polyhedra Capable of Binding Low-Symmetry, Information-Rich Molecular Cargoes
TL;DR: The field of metallosupramolecular chemistry has advanced rapidly in recent years as discussed by the authors , and much work in this area has focused on the formation of hollow self-assembled metal-organic architectures and exploration of the applications of their confined nanospaces.
Journal ArticleDOI
Light-Powered Dissipative Assembly of Diazocine Coordination Cages
TL;DR: This work reports the first Pd-mediated coordination cage based on ligands embedding a diazocine photoswitch, characterized by a combination of NMR, ion mobility ESI-MS, single-crystal X-ray diffraction, and UV–vis absorption studies.
Journal ArticleDOI
Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle.
TL;DR: In this article, a similar correlation between the ligand bent angle and the nuclearity is observed, with larger angles leading to complexes with a higher nuclearity, n. It is well established that the bent angle, α, of a ligand is a decisive factor in the self-assembly process.
Journal ArticleDOI
Sterics and Hydrogen Bonding Control Stereochemistry and Self-Sorting in BINOL-Based Assemblies.
You-Quan Zou,Dawei Zhang,Tanya K. Ronson,Andrew Tarzia,Zifei Lu,Kim E. Jelfs,Jonathan R. Nitschke +6 more
TL;DR: In this paper, the authors demonstrate how the hydrogen bonding ability of a BINOL-based dialdehyde subcomponent dictated the stereochemical outcome of its subsequent self-assembly into one diastereomeric helicate form when bearing free hydroxy groups, and another in the case of its methylated congener.
References
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Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials
Journal ArticleDOI
Functional Molecular Flasks : New Properties and Reactions within Discrete, Self-Assembled Hosts
TL;DR: This Review briefly highlights the various molecular flasks synthesized before focusing on their use as functional molecular containers--specifically for the encapsulation of guest molecules to either engender unusual reactions or unique chemical phenomena.
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Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination
Timothy R. Cook,Peter J. Stang +1 more
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Supramolecular Amphiphiles Based on Host-Guest Molecular Recognition Motifs.
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Self-Assembled M24L48 Polyhedra and Their Sharp Structural Switch upon Subtle Ligand Variation
Qing-Fu Sun,Junji Iwasa,Daichi Ogawa,Yoshitaka Ishido,Sota Sato,Tomoji Ozeki,Yoshihisa Sei,Kentaro Yamaguchi,Makoto Fujita +8 more
TL;DR: It is demonstrated that a mixture of palladium ions and V-shaped bridging ligands can self-assemble into a hollow, nearly spherical polyhedron with 24 vertices and a central diameter of 4 nanometers.
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