Influence of spacer length and rigidity on properties of phosphonium polymers and on their supramolecular assembly with a conjugated polyelectrolyte

Abstract

A series of seven cationic polymers have been prepared wherein the length of spacer between charge-bearing sites has been varied.

A new route to phosphonium polymer network solids via cyclotrimerization

“…Compared with traditional organic frameworks, ionic hypercrosslinked polymers, specifically those involving ionic liquids as monomers, have attracted growing attention. These materials can possess good thermal and chemical stability, properties that can be tuned upon simple counterion exchange, and which can readily form layer‐by‐layer self‐assembled films with other ionic polymers . For example, Yang et al reported an alkaline anion exchange membrane R1 (Scheme ) comprised of copolymerized imidazolium‐functionalized ionic liquids with styrene and acrylonitrile.…”

Intercation spacing and side chain effects on phosphonium polymers: Thermal, supramolecular, and bactericidal properties

“…When visible‐absorbing PELs (Chart ) are employed, the LbL films can be used as finely tuned optical or optoelectronic components . A detailed study on LbL behavior of the LX series polymers (Chart ) and Pc12‐100 confirmed that the spacer flexibility and distance between phosphonium charge bearing units have significant effect on the properties of the PEL and LbL films with polyanions …”

“…An example in which chemical stability is paramount is in an alkaline fuel cell, where the membrane must tolerate extended heating at temperatures up to 80 °C in the presence of aqueous hydroxide. The PEL R3 has proven stable enough for test devices under such conditions, and recent advances in the preparation of tetraarylphosphonium polymers suggest that more advances are on the horizon in this area as structural elements leading to improved stability are identified. PELs also offer advantages in medicinal contexts.…”

“…This is especially surprising in light of the obvious applications (i.e., fluorescent sensors or optoelectronic films) in which these robust materials could find utility. The few examples of chromophore‐derivatized PELs include R2 , EGT1 , SLK1 , and FL1‐2 () . All of these polymers exhibit significant absorption and photoluminescence in the ultraviolet–visible (UV–vis) region of the spectrum, and some exhibit significant solvatochromic effects in response to changing polarity of their environment, making them possible elements of stimuli‐responsive systems …”

“…Although significant strides have been made in understanding backbone effects on PEL properties, the role of side chains has not been systematically addressed. Herein, we described polymers LO (Scheme ), which are structural analogues of the LX series (Chart ), but in which the phenylene units in LX have been replaced with 2,5‐dioctyloxyphenylene units.…”