Novel electrochromic polynorbornenes poly(NBPYTPAM) and poly(HNBPYTPAM), containing electroactive chromophores, were prepared via ring-opening metathesis polymerization (ROMP) from a new norbornene derivative (NBPYTPAM) using Grubbs’ catalyst and followed by hydrogen reduction. The glass transition temperatures (T
g) of poly(NBPYTPAM) and hydrogenated poly(HNBPYTPAM) were 190 and 175 °C, respectively. The cyclic voltammogram of the poly(HNBPYTPAM) film cast onto flexible graphene-coated polyethylene terephthalene (PET) substrates exhibited two reversible oxidation redox couples at 1.0 and 1.9 V. Flexible electrochromic devices were fabricated from the electroactive polymers and graphene-coated PET substrates. The electrochromic characteristics of poly(HNBPYTPAM) showed excellent stability and reversibility, with multistaged color changes from its yellow neutral form to green and then to dark-blue.
The anomeric effect (the tendency of heteroatomic substituents adjacent to a heteroatom within the cyclohexane ring to prefer the axial orientation instead of the sterically less hindered equatorial position) is traditionally explained through either the dipole moment repulsion or the hyperconjugation effect. In this work, by employing our recent work in density functional steric analysis, we provide a novel two-component explanation, which is consistent with the common belief in chemistry that the effect has a stereoelectronic origin. With α-D-glucopyranose as the prototype, we systematically explore its conformational space and generate 32 isomers, leading to a total of 80 axial-equatorial conformation pairs. The energy difference analysis of these pairs shows that while statistically speaking the tendency is valid, the anomeric effect is not always true and can be violated. Three energy components, exchange-correlation, classical electrostatic, and density functional steric, are found to be directly proportional to the total energy difference between axial and equatorial isomers. We also found that the total dipole moment change, not the hyperconjugation effect, is a reasonable indicator of the total energy difference. However, all these correlations alone are not strong enough to provide a compellingly convincing explanation for the general validity of the effect. With the help of strong correlations between energy components, an explanation with two energy components, steric and electrostatic, was proposed in this work. We show that the axial-equatorial energy difference in general, with the anomeric effect as a special case, is dictated by two factors of the stereoelectronic origin, steric hindrance and classical electrostatic interactions, synchronously working together. Another explanation in terms of exchange-correlation and electrostatic interactions has also been obtained in this work.
A metal-organic compound designed with an extremely stable 3D openframework structure enables the aromatic rings in organic ligand to be activated as Na + storage redox sites. A large number of aromatic structures can be constructed into a 3D metal-organic framework for high-capacity electrode materials.
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