Increasing structural and functional complexity in self-assembled coordination cages

Pullen, Sonja; Tessarolo, Jacopo; Clever, Guido H.

doi:10.1039/d1sc01226f

Cited by 219 publications

(199 citation statements)

References 156 publications

Supporting

Mentioning

189

Contrasting

Unclassified

Order By: Relevance

“…The controlled introduction of anisotropy is of particular interest to the development of cages with advanced functionality. [33] For these Pd 2 L 4 systems, a simple definition of anisotropy would be the displacement of the Pd II centres from alignment perpendicular to the PdN 4 planes (Δ Pd , shown inset in Figure 8 a ). For Pd 2 L 4 systems assembled from symmetrical ligands, Δ Pd should be 0 Å.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**

2021

View full text Add to dashboard Cite

Unsymmetrical ditopic ligands can self‐assemble into reduced‐symmetry Pd2L4 metallo‐cages with anisotropic cavities, with implications for high specificity and affinity guest‐binding. Mixtures of cage isomers can form, however, resulting in undesirable system heterogeneity. It is paramount to be able to design components that preferentially form a single isomer. Previous data suggested that computational methods could predict with reasonable accuracy whether unsymmetrical ligands would preferentially self‐assemble into single cage isomers under constraints of geometrical mismatch. We successfully apply a collaborative computational and experimental workflow to mitigate costly trial‐and‐error synthetic approaches. Our rapid computational workflow constructs unsymmetrical ligands and their Pd2L4 cage isomers, ranking the likelihood for exclusively forming cis‐Pd2L4 assemblies. From this narrowed search space, we successfully synthesised four new, low‐symmetry, cis‐Pd2L4 cages.

show abstract

Section: Resultsmentioning

confidence: 99%

“…However, it is expected that through the controlled introduction of asymmetry, cages could be designed with more intricate, anisotropic binding sites with specific shapes and functionalities. [33] …”

Section: Introductionmentioning

confidence: 99%

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**

2021

View full text Add to dashboard Cite

show abstract

“…The complexity of MOCs that are routinely reported has increased dramatically since preliminary studies in the field over thirty years ago ( Pullen et al, 2021 ). Heteroleptic ( Bloch and Clever, 2017 ), mixed-metal ( Li et al, 2015 ) and low symmetry ( Lewis and Crowley, 2020 ) assemblies towards the development of more sophisticated host systems are becoming more commonplace.…”

Section: Conclusion and Future Outlooksmentioning

confidence: 99%

Structural Flexibility in Metal-Organic Cages

Díaz

Lewis

2021

Front. Chem.

View full text Add to dashboard Cite

Metal-organic cages (MOCs) have emerged as a diverse class of molecular hosts with potential utility across a vast spectrum of applications. With advances in single-crystal X-ray diffraction and economic methods of computational structure optimisation, cavity sizes can be readily determined. In combination with a chemist’s intuition, educated guesses about the likelihood of particular guests being bound within these porous structures can be made. Whilst practically very useful, simple rules-of-thumb, such as Rebek’s 55% rule, fail to take into account structural flexibility inherent to MOCs that can allow hosts to significantly adapt their internal cavity. An often unappreciated facet of MOC structures is that, even though relatively rigid building blocks may be employed, conformational freedom can enable large structural changes. If it could be exploited, this flexibility might lead to behavior analogous to the induced-fit of substrates within the active sites of enzymes. To this end, in-roads have already been made to prepare MOCs incorporating ligands with large degrees of conformational freedom. Whilst this may make the constitution of MOCs harder to predict, it has the potential to lead to highly sophisticated and functional synthetic hosts.

show abstract

“…The ability of self-assembled coordination cages-hollow, pseudo-spherical, metalligand assemblies [1][2][3][4][5][6][7]-to bind small-molecule guests in their central cavities has resulted in a wide range of potential applications such as transport and release of 'cargoes' [8][9][10][11] including drug molecules; catalysed reactions of cavity-bound guests whose reactivity is altered [12][13][14][15][16][17][18][19][20][21]; and analysis or sensing of species whose binding in the cavity triggers an optical response [22]. Guests bound inside coordination cages span a huge range from simple anions [23] or solvent molecules [24] via fullerenes [25,26] to small proteins [27,28].…”

Section: Introductionmentioning

confidence: 99%

A Family of Externally-Functionalised Coordination Cages

et al. 2021

View full text Add to dashboard Cite

New synthetic routes are presented to derivatives of a (known) M8L12 cubic coordination cage in which a range of different substituents are attached at the C4 position of the pyridyl rings at either end of the bis(pyrazolyl-pyridine) bridging ligands. The substituents are (i) –CN groups (new ligand LCN), (ii) –CH2OCH2–CCH (containing a terminal alkyne) groups (new ligand LCC); and (iii) –(CH2OCH2)3CH2OMe (tri-ethyleneglycol monomethyl ether) groups (new ligand LPEG). The resulting functionalised ligands combine with M2+ ions (particularly Co2+, Ni2+, Cd2+) to give isostructural [M8L12]16+ cage cores bearing 24 external functional groups; the cages based on LCN (with M2+ = Cd2+) and LCC (with M2+ = Ni2+) have been crystallographically characterised. The value of these is twofold: (i) exterior nitrile or alkene substituents can provide a basis for further synthetic opportunities via ‘Click’ reactions allowing in principle a diverse range of functionalisation of the cage exterior surface; (ii) the exterior –(CH2OCH2)3CH2OMe groups substantially increase cage solubility in both water and in organic solvents, allowing binding constants of cavity-binding guests to be measured under an increased range of conditions.

show abstract

Increasing structural and functional complexity in self-assembled coordination cages

Abstract: This review highlights recent strategies towards the rational synthesis of metallo-supramolecular multicomponent systems, the implementation of functionality and the challenge to create multifunctional assemblies in non-statistical fashion.

Cited by 219 publications

References 156 publications

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**

Structural Flexibility in Metal-Organic Cages

A Family of Externally-Functionalised Coordination Cages

Contact Info

Product

Resources

About

Increasing structural and functional complexity in self-assembled coordination cages

Abstract: This review highlights recent strategies towards the rational synthesis of metallo-supramolecular multicomponent systems, the implementation of functionality and the challenge to create multifunctional assemblies in non-statistical fashion.

Cited by 219 publications

References 156 publications

High‐Throughput Computational Evaluation of Low Symmetry Pd2L4Cages to Aid in System Design**

High‐Throughput Computational Evaluation of Low Symmetry Pd2L4Cages to Aid in System Design**

Structural Flexibility in Metal-Organic Cages

A Family of Externally-Functionalised Coordination Cages

Contact Info

Product

Resources

About

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**

High‐Throughput Computational Evaluation of Low Symmetry Pd₂L₄Cages to Aid in System Design**