The Story of the Little Blue Box: A Tribute to Siegfried Hünig

The tetracationic cyclophane, cyclobis(paraquat-p-phenylene), also known as the little blue box, constitutes a modular receptor that has facilitated the discovery of many host–guest complexes and mechanically interlocked molecules during the past 35 years. Its versatility in binding small π-donors in its tetracationic state, as well as forming trisradical tricationic complexes with viologen radical cations in its doubly reduced bisradical dicationic state, renders it valuable for the construction of various stimuli-responsive materials. Since the first reports in 1988, the little blue box has been featured in over 500 publications in the literature. All this research activity would not have been possible without the seminal contributions carried out by Siegfried Hünig, who not only pioneered the syntheses of viologen-containing cyclophanes, but also revealed their rich redox chemistry in addition to their ability to undergo intramolecular π-dimerization. This Review describes how his pioneering research led to the design and synthesis of the little blue box, and how this redox-active host evolved into the key component of molecular shuttles, switches, and machines.     

Coordination-Driven Selective Formation of D2 Symmetric Octanuclear Organometallic Cages

The coordination-driven self-assembly of organometallic half-sandwich iridium(III)- and rhodium(III)-based building blocks with asymmetric ambidentate pyridyl-carboxylate ligands is described. Despite the potential for obtaining a statistical mixture of multiple products, D₂ symmetric octanuclear cages were formed selectively by taking advantage of the electronic effects emanating from the two types of chelating sites – (O,O’) and (N,N’) – on the tetranuclear building blocks. The metal sources and the lengths of bridging ligands influence the selectivity of the self-assembly. Experimental observations, supported by computational studies, suggest that the D₂ symmetric cages are the thermodynamically favored products. Overall, the results underline the importance of electronic effects on the selectivity of coordination-driven self-assembly, and demonstrate that asymmetric ambidentate ligands can be used to control the design of discrete supramolecular coordination complexes.     

A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework

We report the synthesis of a tetracationic macrocycle which contains two N,N′-bis(methylene)naphthalenediimide units inserted in between the pyridinium rings of the bipyridinium units in cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺ or “blue box”) and describe the investigation of its potential use in materials for organic electronics. The incorporation of the two naphthalenediimide (NDI) units into the constitution of CBPQT⁴⁺, not only changes the supramolecular properties of the tetracation in the solid state, but also has a profound influence on the electrochemical and electronic behavior of the resulting tetracationic macrocycle. In particular, the solid-state (super)structure, investigated by single-crystal X-ray diffraction, reveals the formation of a three-dimensional (3D) supramolecular framework with ca. 2.8 nm diameter one-dimensional (1D) hexagonal channels. Electrochemical studies on solid-state thin films of the macrocycle show that they exhibit semiconducting properties with a redox-conductivity of up to 7.6×10⁻⁴ S m⁻¹. Moreover, EPR and ENDOR spectroscopies show that charge is equally shared between the NDIs within the one-electron reduced state of the NDI-based macrocycle on the time scale of these techniques.     

Concurrent Covalent and Supramolecular Polymerization

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis‐azide‐functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis‐alkyne‐functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β‐cyclodextrin(CD)‐accelerated, cucurbit[6]uril(CB)‐templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss‐cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.     

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC⁴⁺) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC⁴⁺ rings comprise either 1) two bipyridinium (BIPY²⁺) units or 2) a BIPY²⁺ and a diazapyrenium (DAP²⁺) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO₃)₂?2.5 H₂O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY²⁺ units by a DAP²⁺ unit: only the translational isomer in which the DAP²⁺ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.