Defunctionalization of Ester-Substituted Electrochromic Dioxythiophene Polymers

Reeves, Benjamin D.; Unur, Ece; Ananthakrishnan, Nisha; Reynolds, John R.

doi:10.1021/ma070046d

Cited by 88 publications

(92 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…11,35 The solubility of the polymer can be adjusted by using labile groups as well. 41 However, the removal of the labile group is usually very tedious.…”

Section: ■ Introductionmentioning

confidence: 99%

Patternable Conjugated Polymers with Latent Hydrogen-Bonding on the Main Chain

Yang

Chen

et al. 2014

Macromolecules

View full text Add to dashboard Cite

Conjugated polymers with latent hydrogenbonding on the main chain were synthesized using Suzuki coupling reaction. The resulting polymers with latent hydrogen-bonding can be converted to the actual hydrogen-bonded polymers by thermal annealing or UV irradiation. As the hydrogen-bonding sites are fused with π-conjugated units on the polymer backbone, the intermolecular interactions between the polymer chains will be strongly enhanced when the hydrogen-bonds are formed. By removing the protection group and forming hydrogen-bonding, the polymers exhibited a bathochromic shift over those with latent hydrogen-bonding, indicating a hydrogen-bonding-mediated enhancement of π−π stacking. In addition, the fused hydrogen-bond sites and π-conjugated units led to closely packed polymer chains, resulting in insoluble pigment-like polymers. This drastic solubility change from polymers with latent hydrogen-bonding to hydrogen-bonded polymers can be used to pattern conjugated polymers directly. The photolithography of the conjugated polymer with latent hydrogen-bonding was demonstrated, and the patterned electrochromic devices were fabricated and tested. ■ INTRODUCTIONThe organic electronics developed rapidly in the past two decades 1,2 due to their advantages in fabricating lightweight, flexible, and low-cost electronic components. The organic electronic devices such as organic light-emitting devices (OLEDs), organic field-effect transistors (OFETs), and organic photovoltaics (OPVs) have been demonstrated, 3,4 and some have been commercialized. 5,6 Among all the materials for organic electronics, conjugated polymers comprise a class of materials that have the potential to provide low-cost, large-area, and flexible electronic devices. Although the conjugated polymers have been demonstrated in prototype devices that they are in principle suitable for many electronic applications, the implementation of those electronic devices often requires the patterning of conjugated polymers into microregimes to provide various functions. 7−9 For instance, the micropatterning of conjugated polymer is required prerequisite to fabricate the polymer-based OFETs circuit, 10 OLDEs, 11 and electrochromic displays. 12,13 For this purpose, many patterning techniques such as inkjet printing, 14−16 microcontact printing, 17,18 and nanoimprinting 14,19 have been developed to pattern organic electronic materials. Among those techniques, conventional photolithography is of great interest due to the mature industrial scale photolithography instruments from Si-based electronics. Therefore, the conjugated polymers with patterning function that can adopt conventional photolithography technology are highly desired. Photopatterning of conjugated polymer has been explored by some researchers. 20−27 Most works were relied on the approach to directly adjust the solubilities of conjugated polymers through photochemistry, although research of photolithographically patterning conjugated polymers with additional parylene 21 protect layer or special fluorinated photores...

show abstract

“…11,35 The solubility of the polymer can be adjusted by using labile groups as well. 41 However, the removal of the labile group is usually very tedious.…”

Section: ■ Introductionmentioning

confidence: 99%

Patternable Conjugated Polymers with Latent Hydrogen-Bonding on the Main Chain

Yang

Chen

et al. 2014

Macromolecules

View full text Add to dashboard Cite

show abstract

“…10 Reeves et al reported a novel way to process ProDOT-based polymers using defunctionalization route. 11 They used a soluble polymer which can be converted into an insoluble polymer via chemical modification of the pendant side chain.…”

Section: Introductionmentioning

confidence: 99%

Processable, Regioregular, and “Click”able Monomer and Polymers Based on 3,4-Propylenedioxythiophene with Tunable Solubility

2009

View full text Add to dashboard Cite

Click"able monomer and polymers based on 3,4-propylenedioxythiophene, ProDOT, which can be functionalized either at the monomer stage or after the polymerization, were synthesized and characterized for the first time. The solubility of these polymers can be fine-tuned from organic to aqueous solvents by functionalization with an appropriate side chain. In fact, the "click"able functionality allows us to synthesize and chatacterize water-soluble ProDOT-based cationic polymer which were hitherto unknown. Chemical polymerization of propargyl-functionalized ProDOT (ProDOT-propargyl) resulted in an insoluble polymer which could be made water-soluble by reacting it with 1-azido-ethanoic acid sodium salt or 3-azidopropyltrimethylammonium iodide using "click" chemistry. Interestingly, the chemical copolymerization of ProDOT-propargyl with 25 mol % of dihexyl-ProDOT resulted in an organic soluble polymer which was characterized using NMR, FTIR, UV-vis spectroscopy, solution doping, and GPC. This polymer was then used successfully for "click" chemistry in solution. The "click" reaction that was performed on this polymer by using 2-azidoacetic acid sodium salt or 3-azidopropyltrimethylammonium iodide resulted in the complete reversal of solubility from organic solvent of the parent polymer to water solubility of the resulting polymers. In order to study the electrochemical properties, thin films of poly(ProDOT-propargyl) were prepared using electrochemical polymerization and were characterized by electrochemical, spectrochemical, optical switching, and in situ conductance measurements. Electropolymerization resulted in the formation of an electroactive film on the electrode surface. Spectroelectrochemical studies indicated that the polymer switched from opaque blue to a transmissive oxidized state with a contrast of 75%. In situ conductance studies showed a maximum conductance of 0.03 S.

show abstract

“…Conjugated polymers that can be solution-processed and, subsequently, defunctionalized to produce films insoluble in most conventional organic solvents have recently emerged for use in EC and multilayer light-emitting diode (LED) devices, [38] transistors, [39] and photovoltaic cells. [40] In the case of P4c, we found that the spray-cast polymer can be effectively defunctionalized by immersing the films in a 1 M KOH methanol solution for 4 h at 70 8C.…”

mentioning

confidence: 99%