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Conjugated polymers are at the heart of numerous current and emerging technologies. Doping, a process by which charge carriers are introduced, is crucial to their functionality and performance. Despite significant historical context and the exploration of a broad chemical space, doping processes that are activated by formation of a ground-state charge-transfer complex (GS-CTC), which is mediated by the supramolecular hybridization between the frontier molecular orbitals of distinct molecular species, remain poorly understood. There are no clear demonstrations of this phenomena in contemporary donor–acceptor (DA) conjugated polymers (CP). Here, using diketopyrrolopyrrole-based donor–acceptor semiconducting polymers and a -conjugated penta-t-butylpentacyanopentabenzo[25]annulene “cyanostar” macrocycle, we demonstrate the first examples of features that control GS-CTC formation in contemporary DA CP frameworks. Using complementary experimental techniques and theory, we articulate how subtle molecular, electronic, and solid-state features impact supramolecular hybridization of the frontier molecular orbitals and impact the resultant (opto)electronic, magnetic, and transport properties. These studies demonstrate that subtle effects arising from the admixture between distinct -conjugated materials can have dramatic outcomes on properties and performance through modification of the density of states (DOS). These results will enable completely new design rules for organic semiconductors with precise property control. 

We report our discovery of utilizing perhydroxylated dodecaborate clusters ([B 12 (OH) 12 ] 2− ) as a molecular cross-linker to generate a hybrid tungsten oxide material. The reaction of [N n Bu 4 ] 2 [B 12 (OH) 12 ] with WCl 6 , followed by subsequent annealing of the product at 500 °C in air successfully produces a tungsten oxide material cross-linked with B 12 -based clusters. The comprehensive structural study of the produced hybrid material confirms a cross-linked network of intact boron-rich clusters and tungsten oxides. We further demonstrate how these robust B 12 -based clusters in the resulting hybrid tungsten oxide material can effectively preserve the specific capacitance up to 4000 cycles and reduce the charge transfer resistance as well as the response time compared to that of pristine tungsten oxide. Ultimately, this work highlights a promising capability of boron-rich clusters in hybrid metal oxides to obtain fast and stable supercapacitors with high capacitance.