Abstract
Chair 3D Co(II) phosphite frameworks have been prepared by the ionothermal method. It belongs to chiral space group P3221, and the whole framework can be topologically represented as a chiral 4-connected qtz net. It shows a multistep dielectric response arising from the reorientation of Me2-DABCO in the chiral cavities. It can also serve as a pron conductor with high conductivity, 1.71 × 10−3 S cm−1, at room temperature, which is attributed to the formation of denser hydrogen-bonding networks providing efficient proton-transfer pathways.
Highlights
Crystalline materials with open frameworks, such as zeolites and metal-organic frameworks (MOFs), containing a rotatable guest component, have attracted considerable attention owing to their sensitive and controllable responses to external stimuli, such as thermal, pressure, light, or electricity (Kay et al, 2007; Jin et al, 2011; Yan et al, 2012; Hu and Liu, 2014; Huang and Isaacs, 2014; Du et al, 2015)
The (Me2-DABCO)2+ cations reside in the cavities as charge compensation. 1 can serve as an amphidynamic molecular machine (Figure 1C)
Two obvious dielectric peaks were observed at 125°C and 140°C, respectively, which can be attributed to the reorientation of Me2-DABCO in the chiral cavities
Summary
Crystalline materials with open frameworks, such as zeolites and metal-organic frameworks (MOFs), containing a rotatable guest component, have attracted considerable attention owing to their sensitive and controllable responses to external stimuli, such as thermal, pressure, light, or electricity (Kay et al, 2007; Jin et al, 2011; Yan et al, 2012; Hu and Liu, 2014; Huang and Isaacs, 2014; Du et al, 2015). The three-dimensional (3D) crystal lattice can provide well-designed pores for the proton conduction pathway, and the various interactions between the pores and guest molecules. Metal phosphate frameworks are one of the best candidates in new types of proton conduction materials because the porous frameworks are built from robust inorganic units. A chiral 3D metal phosphite framework with a formula [(Me2-DABCO)][Co2(HPO3)3] (compound 1) [Me2-DABCO N,N′-dimethyl-1,4-diazabicyclo(2.2.2)octane] was obtained by the ionothermal method. TG analysis its stability up to 330°C (Supplementary Figure S3)
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