A Series of Tetrathiafulvalene Bismuth Chlorides: Effects of Oxidation States of Cations on Structures and Electric Properties.

Most large organic cations in the low-dimensional hybrid halide perovskites deteriorate the photoelectric conversion efficiency of the cells. Integrating electronically active organic components into hybrid metal halides is an effective method to improve their photoelectric properties. In this work, a series of compounds obtained by hybridizing redox-active tetrakis(methylthio)tetrathiafulvalene (TMT-TTF) with bismuth chloride, formulated as [TMT-TTF][BiCl] ( and ), [TMT-TTF][BiCl] (), [TMT-TTF][BiCl] (), [TMT-TTF][BiCl] (), and {[TMT-TTF][BiCl]} (), were crystallographically characterized. These hybrids exhibit changeable oxidation states of the TTF moiety. The radical cation TTF exists in and , while a mixed-valence TTF/TTF appears in that has never been documented in any compounds and the dication TTF exists in - that has never been introduced into hybrid organic-inorganic materials. The different charged states of the TTF cations lead to various degrees of connectivity of metal chloride anions, which exert a significant effect on the cation-anion arrangement and result in different supramolecular interactions between TMT-TTF and between cations and anions. The changeable oxidation states of the TTF moiety and varying degrees of metal chloride connectivity provide a good comparison among these hybridized bismuth chlorides. The order of conductivity is > > > ≈ ≫ , which results from the synergistic effect of different oxidation states, the packing of TMT-TTF cations, and back charge transfer from the Bi-Cl anion to the TMT-TTF cation. Notably, the electrical conductivity and carrier mobility can be modulated with the fact that compound has the highest performances in the dark, while in light, these properties of and are in turn higher than that of . The order of the photocurrent densities is in accordance with the increase of carrier mobility under irradiation of light. This work is the first systematic study of hybrid metal halides with various oxidation states of TTFs and presents a clear structure-property relationship and offers a fresh view on the design of new perovskite materials at the molecular level.