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Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of S N 2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control. 

Abstract A pre‐formed Meisenheimer complex of a naphthalenediimide (NDI) with tetrabutylammonium fluoride (TBAF) is obtained in a simple way by mixing dibrominated 4,9‐dibromo‐2,7‐bis(2‐octyldodecyl)benzo[lmn][3,8]phenanthroline‐1,3,6,8(2H,7H)‐tetraone and TBAF in solution and used as a dopant for n‐type organic thermoelectrics. Two n‐type polymers PNDIClTVT and PBDOPVTT are synthesized, n‐doped, and characterized as conductive and thermoelectric materials. PNDIClTVT doped with NDI‐TBAF presents a high σ value of 0.20 S cm^–1, a Seebeck coefficient (S) of −1854 µV K^–1, and a power factor (PF) of 67 µW m^–1K^–2, among the highest reported PF in solution‐processed conjugated n‐type polymer thermoelectrics. Using 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine and NDI‐TBAF as co‐dopants, PNDIClTVT has a PF > 35 µW m^–1K^–2; while for PBDOPVTT σ = 0.75 S cm^–1and PF = 58 µW m^–1K^–2. In this study it is found that an ionic adduct together with a neutral dopant improves the performance of n‐type organic thermoelectrics leading to an enhanced power factor, and more generally, the role of such an adduct in polymer doping is also elucidated. 

Abstract Complexation between a viologen radical cation (V^.+) and cyclobis(paraquat‐p‐phenylene) diradical dication (CBPQT^2(.+)) 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 ofV^.+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)^2(.+), i.e.,CBPQN^2(.+). 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 inCBPQN^2(.+)suitable for binding twoMV^.+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 twoMV^.+in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex — namely, [(MV)₂⊂CBPQN]^4(.+)– in MeCN was confirmed by VT¹H NMR, as well as by EPR spectroscopy. The solid‐state superstructure of [(MV)₂⊂CBPQN]^4(.+)reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three differentV^.+, suggesting that localization of the radical‐pairing interactions has a strong influence on the packing of the twoMV^.+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.