Understanding the Interplay of Vacancy, Cation, and Charge Ordering in the Tunable Sc2VO5+δ Defect Fluorite System.

We report the synthesis, structure, and redox behavior of the cation-ordered tetragonal Sc2VO5+δ defect fluorite superstructure previously thought to be the oxygen precise A3+2B4+O5 phase. Four synthesis routes in oxidative, reductive, and inert atmospheres are demonstrated. Ex situ and in situ powder X-ray and neutron diffraction analyses reveal vanadium disproportionation reactions. The structure-reaction map illustrates the oxygen-dependent competition between the tetragonal cation and anion ordered Sc2VO5+δ and the disordered cubic Sc2VO5+δ' (δ < δ' ≤ 0.5) phases as a function of temperature. Oxidation states and oxide stoichiometries were determined with DC magnetometry and XANES experiments. The tetragonal cation ordered Sc2VO5+δ phase with δ = -0.15(2) for as-synthesized samples reveals vanadium charge ordering. V3+ and V4+ cations occupy octahedral sites, whereas V5+ predominantly occupies a tetrahedral site. The paramagnetic 8g{V3+/4+}4 clusters are isolated by diamagnetic 2cV5+ cations. At temperatures below 500 °C the 8g{V3+/4+}4 clusters can be topotactically fine-tuned with varying V3+/V4+ ratios. Above 600 °C the tetragonal structure oxidizes to the cubic Sc2VO5+δ' fluorite phase-its disordered competitor. The investigation of the cation- and anion-ordered Sc-V-O phases, their formation, and thermal stability is important for the design of low-temperature solid state oxide ion conductors and vacancy structures.

Thiophene- and selenophene-based conjugated polymeric mixed ionic/electronic conductors.

Mixed ionic/electronic conductors (MIECs) are desirable materials for next-generation electronic devices and energy storage applications. Polymeric MIECs are attractive from the standpoint that their structure can be controlled and anticipated to have mechanically robust properties. Here, we prepare and investigate conjugated copolymers containing thiophene and selenophene repeat units and their homopolymer counterparts. Specifically, thiophene bearing a triethylene glycol (EG3) side chain was polymerized and copolymerized with dodecyl thiophene/selenophene monomers. The synthesis leads to a class of copolymers that contain either S or Se and are blocky in nature. The Li-ion conductivity of ionically doped copolymers, P3DDT-s-P3(EG3)T and P3DDS-s-P3(EG3)T (9.7 × 10-6 and 8.2 × 10-6 S/cm, respectively), was 3-4 fold higher than that of the ionically doped constituent homopolymer, P3(EG3)T (2.2 × 10-6 S/cm), at ambient conditions. The electronic conductivity of the oxidatively doped copolymers was significantly higher than that of the constituent homopolymer P3(EG3)T, and most notably, P3DDS-s-P3(EG3)T reached ∼7 S/cm, which is the same order of magnitude as poly(3-dodecylthiophene) and poly(3-dodecylselenophene), which are the highest oxidatively doped conductors based on control experiments. Our findings provide implications for designing new MIECs based on copolymerization and the incorporation of heavy atom heterocycles.

Applying Heteroatom Substitution in Organic Photovoltaics.

Poly(3-alkylthiophene) (P3AT) has been a central focus of research on organic photovoltaics (OPVs) for well over a decade. Due to their controlled synthesis P3ATs have proven to be a vital model system for developing an understanding of the effects of polymer structure on optoelectronic properties and blend morphology in bulk heterojunction OPVs. Similar to their thiophene counterparts, selenophene and tellurophene can be polymerized in a controlled manner. As single atom substitution results in significant differences in absorption, charge transport and self-assembly these model systems provide a unique opportunity to probe fundamental structure-property relationships. In this account, we provide an overview of our work on copolymers of thiophene and selenophene and examine how the optoelectronic and morphological behavior of these materials can be strategically adjusted through polymer design. We also highlight recent developments on poly(3-alkyltellurophene) and comment on its future in fundamental and applied studies.

Oxidation promoted self-assembly of π-conjugated polymers.

Self-assembly is an attractive strategy for organizing molecules into ordered structures that can span multiple length scales. Crystallization Driven Self-Assembly (CDSA) involves a block copolymer with a crystallizable core-forming block and an amorphous corona-forming block that aggregate into micelles with a crystalline core in solvents that are selective for the corona block. CDSA requires core- and corona-forming blocks with very different solubilities. This hinders its use for the self-assembly of purely π-conjugated block copolymers since blocks with desirable optoelectronic properties tend to have similar solubilities. Further, this approach is not readily reversible, precluding stimulus-responsive assembly and disassembly. Here, we demonstrate that selective oxidative doping of one block of a fully π-conjugated block copolymer promotes the self-assembly of redox-responsive micelles. Heteroatom substitution in polychalcogenophenes enables the modulation of the intrinsic polymer oxidation potential. We show that oxidized micelles with a narrow size distribution form spontaneously and disassemble in response to a chemical reductant. This method expands the scope of π-conjugated polymers that can undergo controlled self-assembly and introduces reversible, redox-responsive self-assembly of π-conjugated polymers.