Coordination‐Driven Self‐Assembly of a Molecular Knot Comprising Sixteen Crossings

Molecular knots have become highly attractive to chemists because of their prospective properties in mimicking biomolecules and machines. Only a few examples of molecular knots from the billions tabulated by mathematicians have been realized and molecular knots with more than eight crossings have not been reported to date. We report here the coordination‐driven [8+8] self‐assembly of a higher‐generation molecular knot comprising as many as sixteen crossings. Its solid‐state X‐ray crystal structure and multinuclear 2D NMR findings confirmed its architecture and topology. The formation of this molecular knot appears to depend on the functionalities and geometries of donor and acceptor in terms of generating appropriate angles and strong π‐π interactions supported by hydrophobic effects. This study shows coordination‐driven self‐assembly offers a powerful potential means of synthesizing more and more complicated molecular knots and of understanding differences between the properties of knotted and unknotted structures.     

Untying the Photophysics of Quinolinium-Based Molecular Knots and Links

Complex molecular knots and links are still difficult to synthesize and the properties arising from their topology are mostly unknown. Here, we report on a comparative photophysical study carried out on a family of closely related quinolinium-based knots and links to determine the impact exerted by topology on the molecular backbone. Our results indicate that topology has a negligible influence on the behavior of loosely braided molecules, which mostly behave like their unbraided equivalents. On the other hand, tightly braided molecules display distinct features. Their higher packing density results in a pronounced ability to resist deformation, a significant reduction in the solvent-accessible surface area and favors close-range π–π interactions between the quinolinium units and neighboring aromatics. Finally, the sharp alteration in behavior between loosely and tightly braided molecules sheds light on the factors contributing to braiding tightness.     

Designing Artificial 3D Helicates: Unprecedented Self‐Assembly of Homo‐octanuclear Tetrapods with Europium

Herein, we report on the rational design, preparation and characterization of a novel homo‐octanuclear helicate, which results from a spatial extension of the central tetranuclear platform. The 3D supramolecular assembly is obtained by complexing europium(III) with a new hexatopic tripodal ligand. The isolated octanuclear helicate is fully characterized by different methods clearly evidencing the structure predicted with molecular modelling. The ligand preorganization plays a crucial role in a successful self‐assembly process and induces the formation of a well‐defined triple‐stranded helical structure. This prototypal octanuclear edifice accommodating functional lanthanides within a 3D scaffold offers attractive perspectives for further applications.     

Template-Free Self-Assembly of Molecular Trefoil Knots and Double Trefoil Knots Featuring Cp*Rh Building Blocks

Understanding and controlling the topology of self-assembled structures plays a fundamental role in supramolecular chemistry. Herein, the preparation of a series of tetranuclear metallarectangles and hexanuclear trefoil knots featuring Cp*Rh building blocks by template-free self-assembly with four different rigid and flexible ligands is described. Transformations between the trefoil knots and the corresponding macrocycles can be induced by using concentration effects. Remarkably, the hexanuclear trefoil knot 5 was shown to assemble further to provide rare examples of [12+1] heteronuclear double trefoil knots ( 5 a/5 b/5 c/5 d ) through coordination of the amide oxygen atoms to the secondary metal ions Na⁺/K⁺/Ca²⁺/Cd²⁺. The synthetic results are supported by single-crystal XRD.     

Molecular Links and Knots from Naphthalenediimide: A Balance of Weak Interactions

Owing to its unique structural, electronic, spectroscopic, and redox properties, naphthalenediimide (NDI) is a versatile building block for the construction of a wide variety of supramolecular assemblies with diverse structures, properties, and functions. In this Minireview, the synthesis of topologically nontrivial molecular links and knots based on naphthalenediimide‐derived building blocks will be discussed. In particular, the supramolecular forces that contribute to the formation of these molecular links and knots and their interactions will be discussed.     

A Design Strategy for Single‐Stranded Helicates using Pyridine‐Hydrazone Ligands and PbII

The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF₃SO₃)₂?H₂O resulted in some rare examples of discrete single‐stranded helical Pb^II complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF₃SO₃)₂]?CHCl₃ and Pb L2 (CF₃SO₃)₂][Pb L2 CF₃SO₃]CF₃SO₃?CH₃CN, which reflected the high coordination number and effective saturation of Pb^II by the ligands. The reaction of L3 with Pb^II resulted in a dinuclear meso‐helicate [Pb₂ L3 (CF₃SO₃)₂Br]CF₃SO₃?CH₃CN with a stereochemically‐active lone pair on Pb^II. L4 directed single‐stranded helicates with Pb^II, including [Pb₂ L4 (CF₃SO₃)₃]CF₃SO₃?CH₃CN and [Pb₂ L4 CF₃SO₃(CH₃OH)₂](CF₃SO₃)₃?2 CH₃OH?2 H₂O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with Pb^II, including a trinuclear Pb^II complex [Pb₃ L5 (CF₃SO₃)₅]CF₃SO₃?3CH₃CN?Et₂O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with Pb^II.     

Guest‐, Light‐ and Thermally‐Modulated Spin Crossover in [FeII2] Supramolecular Helicates

A new bis(pyrazolylpyridine) ligand (H₂L) has been prepared to form functional [Fe₂(H₂L)₃]⁴⁺ metallohelicates. Changes to the synthesis yield six derivatives, X@[Fe₂(H₂L)₃]X(PF₆)₂?xCH₃OH ( 1 , x=5.7 and X=Cl; 2 , x=4 and X=Br), X@[Fe₂(H₂L)₃]X(PF₆)₂?yCH₃OH?H₂O ( 1 a , y=3 and X=Cl; 2 a , y=1 and X=Br) and X@[Fe₂(H₂L)₃](I₃)₂?3 Et₂O ( 1 b , X=Cl; 2 b , X=Br). Their structure and functional properties are described in detail by single‐crystal X‐ray diffraction experiments at several temperatures. Helicates 1 a and 2 a are obtained from 1 and 2 , respectively, by a single‐crystal‐to‐single‐crystal mechanism. The three possible magnetic states, [LS–LS], [LS–HS], and [HS–HS] can be accessed over large temperature ranges as a result of the structural nonequivalence of the Fe^II centers. The nature of the guest (Cl^? vs. Br^?) shifts the spin crossover (SCO) temperature by roughly 40 K. Also, metastable [LS–HS] or [HS–HS] states are generated through irradiation. All helicates (X@[Fe₂(H₂L)₃])³⁺ persist in solution.     

Securing a Supramolecular Architecture by Tying a Stopper Knot

We report on a rotaxane‐like architecture secured by the in situ tying of an overhand knot in the tris(2,6‐pyridyldicarboxamide) region of the axle through complexation with a lanthanide ion (Lu³⁺). The increase in steric bulk caused by the knotting locks a crown ether onto the thread. Removal of the lutetium ion unties the knot, and when the axle binding site for the ring is deactivated, the macrocycle spontaneously dethreads. When the binding interaction is switched on again, the crown ether rethreads over the 10 nm length of the untangled strand. The overhand knot can be retied, relocking the threaded structure, by once again adding lutetium ions.     

When Self‐Assembly Fails: Stepwise Metal‐Directed Synthesis of [2]Catenanes

On the attempted synthesis of a series of homo‐ and heterotrimetallic [2]catenanes by the self‐assembly of a 2‐(pyridin‐4‐ylmethyl)‐2,7‐diazapyrenium ligand, (ethylenediamine)palladium(II) or platinum(II) nitrate, and a dioxoaryl bis(N‐monoalkyl‐4,4′‐bipyridinium) salt as building blocks, both the one‐pot direct self‐assembly of the components and the so called “magic ring” approach fail to produce the expected trinuclear [2]catenanes under thermodynamically driven conditions. However, one of the target supramolecules is obtained by following a stepwise protocol, consisting of the threading of a dinuclear Pt^II metallacycle and the dioxoaryl bis(N‐monoalkyl‐4,4′‐bipyridinium) axle, followed by kinetically controlled Pt^II‐directed cyclization of the corresponding pseudorotaxane.     

A Bowl‐Shaped Circular Trinuclear Helicate Generated from a TiO4N2 Motif by a Multicomponent Self‐Assembly Approach

The synthesis of a bowl‐shaped trinuclear circular titanium‐based helicate is reported. The strategy allowing access to this neutral architecture is based on a multicomponent self‐assembly approach in which the ligands involved in the process are a bis‐biphenol strand and 2,2′‐ bipyrimidine. By reacting the bis‐biphenol ligand and 2,2′‐bipyrimidine with an equimolar amount [Ti(OiPr)₄], a bowl‐shaped architecture is obtained through the formation of 18 new coordination bonds. This aggregate built from three octahedral TiO₄N₂ nodes displays an unusually high stability in solution compared to related species. In addition, by modifying the stoichiometry of the initial components, two assemblies incorporating two titanium centers bridged by a 2,2′‐bipyrimidine ligand are obtained. The crystal structures of these species are reported.     

Catenanes: Fifty Years of Molecular Links

Half a century after Schill and Lüttringhaus carried out the first directed synthesis of a [2]catenane, a plethora of strategies now exist for the construction of molecular Hopf links (singly interlocked rings), the simplest type of catenane. The precision and effectiveness with which suitable templates and/or noncovalent interactions can arrange building blocks has also enabled the synthesis of intricate and often beautiful higher order interlocked systems, including Solomon links, Borromean rings, and a Star of David catenane. This Review outlines the diverse strategies that exist for synthesizing catenanes in the 21st century and examines their emerging applications and the challenges that still exist for the synthesis of more complex topologies.     

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host–guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low‐symmetry imine cages. Whether a low‐energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high‐symmetry cages‐and the same aldehyde generates low‐symmetry socially self‐sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low‐symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self‐sorting.     

Boronic Acids in Molecular Self‐Assembly

The reversibility of boronic acid and diol interaction makes it an ideal candidate for the design of self‐assembled molecular structures. Reversibility is required to ensure that the thermodynamically most stable structure is formed. Reversibility also ensures that any errors produced during the assembly process are not permanent.