Identification of a Heteroleptic Pd6L6L'6 Coordination Cage by Screening of a Virtual Combinatorial Library.

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 [PdnL2n](BF4)2n complexes was prepared by mixing six different dipyridyl ligands with substoichiometric amounts of [Pd(CH3CN)4](BF4)2. Analysis of the equilibrated reaction mixture revealed the preferential formation of a heteroleptic [Pd6L6L'6](BF4)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 Pd3L3 macrocycles bridged by six L' ligands. A related but significantly larger [Pd6L6L'6](BF4)12 cage was obtained by using metalloligands instead of organic dipyridyl ligands.

Two-Step Synthesis of Linear and Bent Dicarboxylic Acid Metalloligands with Lengths of up to 3 nm.

Nanometer-sized polycarboxylate ligands are interesting building blocks for metallasupramolecular chemistry, but access to these compounds is often limited by complicated synthetic pathways. Here, we describe a simple two-step protocol, which allows preparing linear and bent dicarboxylate ligands with lengths of up to 3 nm from commercially available compounds. The ligands are prepared by iron-templated polycondensation reactions involving arylboronic acids and nioxime. The final products contain two iron clathrochelate complexes and two terminal carboxyphenylene groups. To demonstrate that the new ligands are suitable for the construction of more complex molecular nanostructures, we have prepared a Cu-based metal-organic polyhedron, which represents the largest M4L4 cage described so far.

Palladium-Based Metal-Ligand Assemblies: The Contrasting Behavior upon Addition of Pyridine or Acid.

The stability of five different [Pd n(N-donor) m]2 n+ 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 pH-controlled switching between different metallosupramolecular structures.

Clathrochelate Metalloligands in Supramolecular Chemistry and Materials Science.

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.

Ligand Aspect Ratio as a Decisive Factor for the Self-Assembly of Coordination Cages.

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.

A twist-bend nematic phase driven by hydrogen bonding.

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.

Reversible disassembly of metallasupramolecular structures mediated by a metastable-state photoacid.

The addition of a metastable-state photoacid to solutions containing metal-ligand assemblies renders the systems light responsive. Upon irradiation, proton transfer from the photoacid to the ligand is observed, resulting in disassembly of the metallasupramolecular structure. In the dark, the process is fully reversed. Light-induced switching was demonstrated for six different metal-ligand assemblies containing PdII, PtII or RuII complexes and bridging polypyridyl ligands. The methodology allows liberating guest molecules with light.

Inflating face-capped Pd6L8 coordination cages.

Tritopic metalloligands were used to form two Pd6L8-type coordination cages. With molecular weights of more than 15 kDa and PdPd distances of up to 4.2 nm, these complexes are among the largest palladium cages described to date.

PdII2L4-type coordination cages up to three nanometers in size.

The utilization of large ligands in coordination-based self-assembly represents an attractive strategy for the construction of supramolecular assemblies more than two nanometers in size. However, the implementation of this strategy is hampered by the fact that the preparation of such ligands often requires substantial synthetic effort. Herein, we describe a simple one-step protocol, which allows large bipyridyl ligands with a bent shape to be synthesized from easily accessible and/or commercially available starting materials. The ligands were used to construct PdII2L4-type coordination cages of unprecedented size. Furthermore, we provide evidence that these cages may be stabilized by close intramolecular packing of lipophilic ligand side chains. Packing effects of this kind are frequently encountered in protein assemblies, but they are seldom used as a design element in metallasupramolecular chemistry.