It is possible to control the geometry and the composition of metallasupramolecular assemblies via the aspect ratio of their ligands. This point is demonstrated for a series of iron- and palladium-based coordination cages. Functionalized clathrochelate complexes with variable aspect ratios were used as rod-like metalloligands. A cubic Fe(II)8L12 cage was obtained from a metalloligand with an intermediate aspect ratio. By increasing the length or by decreasing the width of the ligand, the self-assembly process resulted in the clean formation of tetrahedral Fe(II)4L6 cages instead of cubic cages. In a related fashion, it was possible to control the geometry of Pd(II)-based coordination cages. A metalloligand with a large aspect ratio gave an entropically favored tetrahedral Pd(II)4L8 assembly, whereas an octahedral Pd(II)6L12 cage was formed with a ligand of the same length but with an increased width. The aspect ratio can also be used to control the composition of dynamic mixtures of Pd(II) cages. Out of two metalloligands with only marginally different aspect ratios, one gave rise to a self-sorted collection of Pd(II)4L8 and Pd(II)6L12 cages, whereas the other did not.

The liquid crystalline phase behavior of 4-[6-(4'-cyanobiphenyl-4-yl)hexyloxy]benzoic acid (CB6OBA) and 4-[5-(4'-cyanobiphenyl-4-yloxy)pentyloxy]benzoic acid (CBO5OBA) is described. Both acids show an enantiotropic nematic phase attributed to the formation of supramolecular complexes by hydrogen bonding between the benzoic acid units. In addition, CB6OBA provides the first example of hydrogen bonding driving the formation of the twist-bend nematic phase. The observation of the twist-bend nematic phase for CB6OBA, but not CBO5OBA, is attributed to the more bent molecular shape of the complexes formed by the former, reinforcing the view that shape is a key factor in stabilizing this new phase. Temperature-dependent FTIR spectroscopy reveals differences in hydrogen bonding between the two nematic phases shown by CB6OBA which suggest that the open hydrogen-bonded complexes may play an important role in stabilizing the helical arrangement found in the twist-bend nematic phase.

The term "clathrochelate" describes a complex in which a coordinatively saturated metal ion is surrounded by a macropolycyclic ligand. First examples of clathrochelate complexes were reported 50 years ago. Meanwhile, the synthesis and reactivity of clathrochelates have been investigated in detail, and numerous applications have been explored. In this Account, we summarize work on the utilization of transition metal clathrochelates as metalloligands in supramolecular chemistry and materials science, with special focus on results from our group. First, we discuss the chemistry of boron-capped clathrochelates. These complexes are facile to synthesize by metal-templated condensation reactions. The synthesis is modular, and it is straightforward to implement structural variations. Importantly, it is possible to attach functional groups such as amines, pyridines, or carboxylic acids to the ligand periphery. Other noteworthy features of boron-capped clathrochelates are high thermodynamic and kinetic stability, tunable redox potential, and good solubility. Next, we show that clathrochelate-based metalloligands can be used to build molecularly defined metal-ligand assemblies of nanoscale dimensions. Different molecular architectures are described, including coordination cages with unusual gyrobifastigium or square orthobicupola-like structures. Metalloligands containing multiple clathrochelate complexes are particularly well suited to build large metal-ligand assemblies (>3 nm) with minimal synthetic efforts. Boron-capped clathrochelates have also been investigated in the context of materials chemistry. Linear or cross-linked clathrochelate polymers were found to display permanent porosity. Furthermore, such polymers were used to prepare conducting films on electrodes. Clathrochelate metalloligands are well suited to prepare metal-organic frameworks (MOFs). The high stability of clathrochelates ensures compatibility with harsh reaction conditions, and it mitigates potential problems such as exchange reactions. Boron-capped clathrochelates can be decorated with functional groups in lateral and apical position, and it is possible to use these complexes as multiconnected nodes in polymeric structures. Overall, we hope to convey the utility of clathrochelate complexes in supramolecular chemistry and materials science. The work published thus far gives a first glimpse of the potential of these compounds, but there are other directions, which are waiting to be explored. For example, it will be interesting to study the properties of nanostructures based on chiral clathrochelate complexes. Furthermore, the redox and magnetic properties of clathrochelates may give rise to novel functional materials. Given that clathrochelates are straightforward to prepare, we hope that others will join the efforts to explore the supramolecular and materials chemistry of these interesting molecular building blocks.

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The liquid crystalline phase behavior of 4‐[6‐(4′‐cyanobiphenyl‐4‐yl)hexyloxy]benzoic acid (CB6OBA) and 4‐[5‐(4′‐cyanobiphenyl‐4‐yloxy)pentyloxy]benzoic acid (CBO5OBA) is described. Both acids show an enantiotropic nematic phase attributed to the formation of supramolecular complexes by hydrogen bonding between the benzoic acid units. In addition, CB6OBA provides the first example of hydrogen bonding driving the formation of the twist‐bend nematic phase. The observation of the twist‐bend nematic phase for CB6OBA, but not CBO5OBA, is attributed to the more bent molecular shape of the complexes formed by the former, reinforcing the view that shape is a key factor in stabilizing this new phase. Temperature‐dependent FTIR spectroscopy reveals differences in hydrogen bonding between the two nematic phases shown by CB6OBA which suggest that the open hydrogen‐bonded complexes may play an important role in stabilizing the helical arrangement found in the twist‐bend nematic phase.

Only stable in the dark: when mixed with a metastable-state photoacid, metallasupramolecular structures become light sensitive. The photo-induced disassembly of the structures is reversed when the light is switched off.

The design of structurally defined heteroleptic coordination cages is a challenging task, and only few examples are known to date. Here we describe a selection approach that allowed the identification of a novel hexanuclear Pd cage containing two types of dipyridyl ligands. A virtual combinatorial library of [Pd n L 2n ](BF 4 ) 2n complexes was prepared by mixing six different dipyridyl ligands with substoichiometric amounts of [Pd(CH 3 CN) 4 ](BF 4 ) 2 . Analysis of the equilibrated reaction mixture revealed the preferential formation of a heteroleptic [Pd 6 L 6 L′ 6 ](BF 4 ) 12 assembly. The complex was prepared on a preparative scale by a targeted synthesis, and its structure was elucidated by single-crystal X-ray diffraction. It features an unprecedented trigonal-antiprismatic cage structure with two triangular Pd 3 L 3 macrocycles bridged by six L′ ligands. A related but significantly larger [Pd 6 L 6 L′ 6 ](BF 4 ) 12 cage was obtained by using metalloligands instead of organic dipyridyl ligands.

The stability of five different [Pd n (Ndonor) m ] 2n+ assemblies was examined by performing disassembly experiments with pyridine and with trifluoroacetic acid. Pyridine-induced disassembly was found to be most pronounced for Pd complexes containing N-donor ligands of low basicity. At the same time, these assemblies displayed high acid resistance. The contrasting stability in the presence of acid or pyridine can be used for the pHcontrolled switching between different metallosupramolecular structures.