Molecular ferroelectrics are attracting tremendous interest because of their easy and environmentally friendly processing, light weight, low acoustical impedance, and mechanical flexibility, which are viable alternatives or supplements to conventional ceramic ferroelectrics. However, reports of ceramic-like molecular ferroelectrics that can be applied in the polycrystalline form have been scarce. Here, according to the "quasi-spherical theory", we successfully synthesized a ceramic-like molecular ferroelectric with an m3mFmm2 type phase transition at 357 K, 1,5-diazabicyclo[3.2.1]octonium tetrafluoroborate ([3.2.1-dabco]BF 4 ), which can show excellent ferroelectric performance in the polycrystalline thin-film form at room temperature. On the basis of the reported molecular ferroelectric [2.2.2-dabco]BF 4 (2.2.2-dabco = 1,4-diazabicyclo[2.2.2]octonium) with an Aizu notation of 4/mmmFmm2 and two polar axes, we changed the [2.2.2-dabco] + cation to the [3.2.1-dabco] + cation to reduce the molecular symmetry and keep the quasi-spherical shape simultaneously, making the number of polar axes up to six. Moreover, the spontaneous polarization P s gets successfully increased from 4.9 μC cm −2 in [2.2.2-dabco]BF 4 to 5.5 μC cm −2 in [3.2.1-dabco]BF 4 . This precise molecular design strategy offers an efficient pathway to design ceramic-like molecular ferroelectrics.
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