Selective formation of multicomponent structures via the self-assembly of numerous building blocks is ubiquitous in biological systems but challenging to emulate synthetically. More components introduce additional possibilities for kinetic intermediates with trap-state ability, hampering access to desired products. In covalent chemistry, templates, reagents and catalysts are applied to create alternative pathways for desired product formation. Analogously, we enlist exo-templating to mould the formation of large, multicomponent supramolecular structures. Specifically, a charged ring docks at 1,5-dioxynaphthalene stations within exo-functionalized building blocks to promote formation of cuboctahedral Pd12L24 nanospheres via exoskeletal templating. With the exo-templating ring present, nanosphere formation occurs via small Pdx–Ly oligomers, while in the absence of the ring a Pdx–Ly polymer resting state rapidly evolves, from which nanosphere formation occurs slowly. We demonstrate a form of kinetic templating—via intermediate destabilization—resembling properties observed in catalysis. Importantly, unlike typically employed endo-templates, we demonstrate that exo-templating is particularly suited for larger, complex, self-assembled structures.

We present the design and comprehensive investigation of stable para-substituted triarylamine–2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) radical ion pairs (RIPs) generated via single-electron transfer (SET). We quantified the degree of SET in both solution and solid phases, utilising a suite of spectroscopic techniques including IR, EPR, NMR, and single-crystal X-ray diffraction (SC–XRD). Our findings reveal that the extent of SET is significantly influenced by the nature of the substituents (MeO > tBu > Br) and the polarity of the solvent (MeCN > DCM > toluene). The radical ion pair [(pMeOPh)3N]⋅+[DDQ]⋅− was unambiguously identified using EPR and UV–vis spectroscopy, and its structure was confirmed by SC–XRD. Detailed analysis indicates an open-shell singlet ground state with a thermally accessible triplet state, as corroborated by EPR, magnetic susceptibility measurements, and DFT calculations. This study offers crucial insights into the mechanistic pathways of RIP formation and tuning both in solution and solid states, laying the groundwork for future exploration of their reactivity and potential applications.