Tunable control of the performance of aqueous-based electrochemical devices by post-polymerization functionalization.

Functionalized polymeric mixed ionic-electronic conductors (PMIECs) are highly desired for the development of electrochemical applications, yet are hindered by the limited conventional synthesis techniques. Here, we propose a "graft-onto-polymer" synthesis strategy by post-polymerization functionalization (GOP-PPF) to prepare a family of PMIECs sharing the same backbone while functionalized with varying ethylene glycol (EG) compositions (two, four, and six EG repeating units). Unlike the typical procedure, GOP-PPF uses a nucleophilic aromatic substitution reaction for the facile and versatile attachment of functional units to a pre-synthesized conjugated-polymer precursor. Importantly, these redox-active PMIECs are investigated as a platform for energy storage devices and organic electrochemical transistors (OECTs) in aqueous media. The ion diffusivity, charge mobility and charge-storage capacity can be significantly improved by optimizing the EG composition. Specifically, g2T2-gBT6 containing the highest EG density gives the highest charge-storage capacity exceeding 180 F g-1 among the polymer series, resulting from the improved ion diffusivity. Moreover, g2T2-gBT4 with four EG repeating units exhibits a superior performance compared to its two analogues in OECTs, associated with a high µC* up to 359 F V-1 cm-1 s-1, owing to the optimal balance between ionic-electronic coupling and charge mobility. Through the GOP-PPF, PMIECs can be tailored to access desirable performance metrics at the molecular level.

Backbone coplanarity manipulation via hydrogen bonding to boost the n-type performance of polymeric mixed conductors operating in aqueous electrolyte.

The development of high-performance n-type semiconducting polymers remains a significant challenge. Reported here is the construction of a coplanar backbone via intramolecular hydrogen bonds to dramatically enhance the performance of n-type polymeric mixed conductors operating in aqueous electrolyte. Specifically, glycolated naphthalene tetracarboxylicdiimide (gNDI) couples with vinylene and thiophene to give gNDI-V and gNDI-T, respectively. The hydrogen bonding functionalities are fused to the backbone to ensure a more coplanar backbone and much tighter π-π stacking of gNDI-V than gNDI-T, which is evidenced by density functional theory simulations and grazing-incidence wide-angle X-ray scattering. Importantly, these copolymers are fabricated as the active layer of the aqueous-based electrochromic devices and organic electrochemical transistors (OECTs). gNDI-V exhibits a larger electrochromic contrast (ΔT = 30%) and a higher coloration efficiency (1988 cm2 C-1) than gNDI-T owing to its more efficient ionic-electronic coupling. Moreover, gNDI-V gives the highest electron mobility (0.014 cm2 V-1 s-1) and µC* (2.31 FV-1 cm-1 s-1) reported to date for NDI-based copolymers in OECTs, attributed to the improved thin-film crystallinity and molecular packing promoted by hydrogen bonds. Overall, this work marks a remarkable advance in the n-type polymeric mixed conductors and the hydrogen bond functionalization strategy opens up an avenue to access desirable performance metrics for aqueous-based electrochemical devices.

Tunable Control of the Hydrophilicity and Wettability of Conjugated Polymers by a Postpolymerization Modification Approach.

A facile method to prepare hydrophilic polymers by a postpolymerization nucleophillic aromatic substitution reaction of fluoride on an emissive conjugated polymer (CP) backbone is reported. Quantitative functionalization by a series of monofunctionalized ethylene glycol oligomers, from dimer to hexamer, as well as with high molecular weight polyethylene glycol is demonstrated. The length of the ethylene glycol sidechains is shown to have a direct impact on the surface wettability of the polymer, as well as its solubility in polar solvents. However, the energetics and band gap of the CPs remain essentially constant. This method therefore allows an easy way to modulate the wettability and solubility of CP materials for a diverse series of applications.

Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane.

Modification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has not been studied for the modification of conjugated polymers used in organic electronics. Crucial questions regarding selectivity and reaction time waited to be addressed. Here, we show that the reaction is highly selective and complete within just a few minutes when using dimethyldioxirane (DMDO) for the oxidation of thioalkyl substituents attached to the well-investigated conjugated polymers poly(9-(1-octylnonyl)carbazole-alt-4,7-dithienylbenzothiadiazole) (PCDTBT) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The selectivity was confirmed by comparison with polymers obtained from pre-oxidized monomers and by control experiments using related polymers without thioalkyl substituents. Using DMDO, the oxidation yields acetone as the only side-product, which reduces the work-up to mere evaporation of solvents and excessive reagent. Our results show that this oxidation is an exciting method for the preparation of electron-deficient conjugated polymers. It may even allow the preparation of electron acceptors for solar cells directly from the electron donors.

Post-polymerisation functionalisation of conjugated polymer backbones and its application in multi-functional emissive nanoparticles.

Backbone functionalisation of conjugated polymers is crucial to their performance in many applications, from electronic displays to nanoparticle biosensors, yet there are limited approaches to introduce functionality. To address this challenge we have developed a method for the direct modification of the aromatic backbone of a conjugated polymer, post-polymerisation. This is achieved via a quantitative nucleophilic aromatic substitution (SNAr) reaction on a range of fluorinated electron-deficient comonomers. The method allows for facile tuning of the physical and optoelectronic properties within a batch of consistent molecular weight and dispersity. It also enables the introduction of multiple different functional groups onto the polymer backbone in a controlled manner. To demonstrate the versatility of this reaction, we designed and synthesised a range of emissive poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT)-based polymers for the creation of mono and multifunctional semiconducting polymer nanoparticles (SPNs) capable of two orthogonal bioconjugation reactions on the same surface.