Radically Enhanced Dual Recognition.

Complexation between a viologen radical cation (V ) and cyclobis(paraquat-p-phenylene) diradical dication (CBPQT ) has been investigated and utilized extensively in the construction of mechanically interlocked molecules (MIMs) and artificial molecular machines (AMMs). The selective recognition of a pair of V using radical-pairing interactions, however, remains a formidable challenge. Herein, we report the efficient encapsulation of two methyl viologen radical cations (MV ) in a size-matched bisradical dicationic host - namely, cyclobis(paraquat-2,6-naphthalene) , i.e., CBPQN . Central to this dual recognition process was the choice of 2,6-bismethylenenaphthalene linkers for incorporation into the bisradical dicationic host. They provide the space between the two bipyridinium radical cations in CBPQN suitable for binding two MV with relatively short (3.05-3.25 Å) radical-pairing distances. The size-matched bisradical dicationic host was found to exhibit highly selective and cooperative association with the two MV in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex - namely, [(MV) ⊂CBPQN] - in MeCN was confirmed by VT H NMR, as well as by EPR spectroscopy. The solid-state superstructure of [(MV) ⊂CBPQN] reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three different V , suggesting that localization of the radical-pairing interactions has a strong influence on the packing of the two MV inside the bisradical dicationic host. Our findings constitute a rare example of binding two radical guests with high affinity and cooperativity using host-guest radical-pairing interactions. Moreover, they open up possibilities of harnessing the tetrakisradical tetracationic inclusion complex as a new, orthogonal and redox-switchable recognition motif for the construction of MIMs and AMMs.