Specific Ion Effects of Azobenzene Salts on Photoresponse of PNIPAm in Aqueous Solutions.

Ionic species are important to dominate phase separation behaviors of poly(N-isopropylacrylamide) (PNIPAm) in aqueous solutions. Herein, photoresponsive azobenzene-based salts with various ions are prepared and their photoresponsive ion effects on clouding temperatures (TcpS ) of PNIPAm in aqueous solutions are explored. It is found that, despite of various structures of anions and cations, trans-TcpS under vis light irradiation are always higher than cis-TcpS under UV irradiation. Particularly, Hofmeister effect of anions on TcpS is roughly observed. For example, azobenzene with kosmotropic CO3 2- gives the lowest cis-Tcp while in use of typical chaotropic anions, such as ClO4 - , azobenzene isomerization less affects values of Tcp s. In another hand, azobenzene-based metallic salts containing lithium, sodium, and potassium cations also demonstrate photoresponsive Hofmeister effect. Trans-metallic azobenzene demonstrates a chaotropic effect on Tcp s while UV induces kosmotropic behaviors on TcpS . Additionally, ionic conduction of the solution along with photoresponsive phase separations is also investigated and PNIPAm aggregations induce a sharp reduction of ion conduction during UV light illumination.

Reversible Ion-Conducting Switch by Azobenzene Molecule with Light-Controlled Sol-Gel Transitions of the PNIPAm Ion Gel.

Exploring a simple, on-demanding method of manipulating ionic conduction of ionic liquids with large amplitudes is a challenging task. Here, a reversible ion-conducting switch was obtained based on photoswitchable sol-gel transitions. The device was successfully applied in an electronic circuit to switch it on/off. The ion gel was prepared by directly mixing following individual components: azobenzene (Azo), poly(N-isopropylacrylamide) (PNIPAm), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]). The mixture is denoted as Azo/PNIPAm/[C2mim][NTf2]. The framework of this gel structure was particularly designed as an analogue to the physical mode of control theory: sensor/amplification/action. Light-induced isomerization of Azo acts as the light sensor to trigger the macroscopic sol-gel transition of PNIPAm assemblies. Such transition works as the amplification, which significantly affects the ionic movements, resulting in high-amplitude switching behavior. A photoswitchable ionic conductive device was demonstrated as action in this paper. Under UV irradiation, the sol-like state of Azo/PNIPAm/[C2mim][NTf2] provided a higher ion conduction (around 1 mS/cm) while being exposed to visible light, and a lower ion conduction (0.04 mS/cm) was observed in the gel state. This photoswitchable ion conductivity device was integrated to a well-designed logic gate to switch circuits on or off. This confirms the possible practical application of the sol-gel device, which outputs stable and detectable electrical signals. The research here demonstrates a simple but effective strategy to control the ionic movements, which can be applied in optoelectronic devices. The principle can be used to design different types of molecular optoelectronic switches.