Host–Guest chemistry based on solid-state pillar[n]arenes

Fullerene chemistry has come a long way since 1990, when the first bulk production of C60 was reported. In the past decade, progress in supramolecular chemistry has opened some remarkable and previously unexpected opportunities regarding the selective (multiple) functionalization of fullerenes and their (self)assembly into larger structures and frameworks. The purpose of this review article is to provide a comprehensive overview of these recent developments. We describe how macrocycles and cages that bind strongly to C60 can be used to block undesired addition patterns and thus allow the selective preparation of single-isomer addition products. We also discuss how the emergence of highly shape-persistent macrocycles has opened opportunities for the study of photoactive fullerene dyads and triads as well as the preparation of mechanically interlocked compounds. The preparation of two- or three-dimensional fullerene materials is another research area that has seen remarkable progress over the past few years. Due to the rapidly decreasing price of C60 and C70, we believe that these achievements will translate into all fields where fullerenes have traditionally (third-generation solar cells) and more recently been applied (catalysis, spintronics).

Recent advances in supramolecular fullerene chemistry.

Synthetic macrocycles have worked as the principal tools for supramolecular chemistry, and also greatly extended the scope of organic charge transfer (CT) complexes as well as their practical value in solid state during the past few years. In this Minireview, we summarize the research progress on the macrocycles-based crystalline supramolecular assemblies primarily driven by intermolecular CT interactions (a.k.a. macrocycles-based crystalline CT assemblies, MCCAs for short), which are classified by their different types of donor-acceptor (D-A) constituent elements, including simplex macrocyclic hosts, heterogeneous macrocyclic hosts and host-guest D-A pairs. Particular attention will be focused on their diversiform functions and applications, as well as underlying CT mechanisms from the perspective of crystal engineering. Finally, the remaining challenges and prospects are outlined.

Macrocycle-Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge-Transfer Interactions.

Unprecedented interheteromacrocyclic hosts charge transfer (CT) crystals were generated by cooling organic solutions containing p-dimethoxybenzene-constituted pillar[5]arene (P5A) and p-benzoquinone-constituted pillar[5]quinone (P5Q). Despite the weak CT interaction known between p-dimethoxybenzene and p-benzoquinone and the lack of formation of CT complexes between P5A and P5Q in the solution phase, CT cocrystals between P5A and P5Q were formed with solvent molecules included into the hosts' cavities. Such a cocrystallization arises from an elegant synergy between the CT interaction and solvent-binding-promoted crystallization. The interhetero hosts CT crystals were studied by optical and electron microscopic techniques, X-ray powder diffraction, solid-state NMR, UV-vis, IR spectroscopic studies, and X-ray single-crystal studies. The solvent complexation was critical for formation of the supramolecular CT microcrystals. The CT absorption bands faded upon removing the solvent molecules under vacuum, but they could be recovered by reuptake of the solvent molecules. Intriguingly, the CT absorption bands and uptake kinetics are distinguishably different for various organic solvents, thus providing a unique way to distinguish between different commonly used chemicals.

Guest-Binding-Induced Interhetero Hosts Charge Transfer Crystallization: Selective Coloration of Commonly Used Organic Solvents.

Variable stoichiometry co-crystals are important in solid-state supramolecular chemistry as they allow studies of structure-property relationships while permitting the synthesis of new scaffolds using identical synthons. In this work, we extend the concept of variable stoichiometry co-crystals into the realm of pillararene chemistry and show that this permits the rational construction of a diverse set of supramolecular structures in the solid state. Specifically, we report a series of variable stoichiometry co-crystals based on pillar[n]arenes and tetracyanobenzene (TCNB) and show that the combination of in-cavity complexation by pillar[n]arenes (n = 5,6) and outside binding with TCNB allows several types of co-crystals with different self-assembled superstructures to be isolated. The variable stoichiometry co-crystals of this study display different solid-state physicochemical properties, including colors and luminescence features. Among these pillar[n]arene-based co-crystals, we discovered unique crystallographic architectures wherein two sets of individual host-guest complexes co-exist in the solid state. These mixed co-crystal systems allow for vapochromic-based detection of n-bromoalkanes. This work highlights a new strategy for the construction of self-assembled superstructures in the solid state and for tuning their intrinsic characteristics, including their luminescent and substrate-responsive features.

Pillararene-Based Variable Stoichiometry Co-Crystallization: A Versatile Approach to Diversified Solid-State Superstructures.

Fulleropillar[4]arene: The Synthesis and Complexation Properties.

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Guest-Binding-Induced Interhetero Hosts Charge Transfer Crystallization: Selective Coloration of Commonly Used Organic Solvents.

Fulleropillar[4]arene: The Synthesis and Complexation Properties.