Polymer Valence Isomerism: Poly(Dewar-o-xylylene)s

Abstract

Poly( o-xylylene) (POX) has long been a challenging synthetic target despite its simple structure and potentially useful physical properties. In this report, we demonstrate a valence isomer strategy that leads to the formation of high molecular weight POX via an intermediate polymer of a unique structure, namely poly(Dewar- o-xylylene) (PDOX). We show that the free radical polymerization of highly strained Dewar- o-xylylene (DOX) monomer afforded PDOX, a material with a high density of Dewar benzene units in the backbone through ring-retaining propagation. The thermal- and photoinduced isomerizations of PDOX to produce POX were investigated. This chemistry yields POXs that are difficult to obtain using traditional methods. Moreover, it also provides a potential entry into new reconfigurable materials featuring highly efficient postpolymerization main chain structural transformations.

Layer‐by‐layer assembly and electrically controlled disassembly of water‐soluble Poly(3,4‐ethylenedioxythiophene) derivatives for bioelectronic interface

“…Our results are consistent with the previous studies. [ 41–43 ] We then measured the absorption intensity at a fixed wavelength of 582 and 522 nm for PEDOT‐NMe 3 and PEDOT‐SO 3 , respectively (Figure S7), which complemented the absorption results. Upon oxidation, a consistent decrease in the absorption upon oxidation and a consistent increase upon reduction was observed for both polymers.…”

Bicyclo[2.2.0]hexene derivatives as a proaromatic platform for group transfer and chemical sensing

“…The fate of the resulting radical cation III would depend on the nature of R group, which might engage either radical or ionic group transfer through different fragmentation pathways. To circumvent the synthesis and stability issues mentioned above, a valence isomerism strategy was conceived 30 . We envisioned bicyclo[2.2.0]hexene (BCH) derivatives as stable and easily accessible surrogates for 1,3-CHD derivatives that possess a similar oxidation potential.…”

C(sp3)—C(sp3) Bond Formation via Transition-Metal Mediated and Catalyzed Reductive Homocouplings

“…2016 年, Wang 课题组 [71] 基于铜参与的苄基自由 基偶联反应, 成功制备了一系列 PPX 衍生物(Scheme 27a). 在过量的单质铜和配体存在条件下, 各种结构的 [74] . 2020 年, Zhao 课题 组 [75] 基于邻二苄溴的还原自偶联反应, 实现了 POX 及 多种衍生物的合成(Scheme 28a).…”