Conjugated microporous polymers for near-infrared photothermal control of shape change

Abstract

Herein, a facile and highly efficient synthetic method to prepare organic photothermal materials with high photo-stability and outstanding photothermal performance is reported. Through direct polymerization of commercial aromatic monomers in the presence of anhydrous aluminium chloride and dichloromethane, four kinds of conjugated microporous polymers (CMPs) were obtained. Detailed structural analysis confirmed that the resultant CMPs possessed abundant micropores with an extended π-conjugated skeleton. Under near-infrared (NIR) light irradiation (808 nm, 1.0 W cm −2 ), all the CMPs showed fast heating-up behavior with their maximum temperatures higher than 150°C. Moreover, the efficiency of photothermal conversion (η) of the CMPs was found to increase linearly with the increase in the number of conjugated benzene rings within the monomer. Poly-TPE from tetraphenylethylene (TPE) and Poly-TP from o-terphenyl (TP) showed high η values of over 47%. Poly-TPE was additionally used as a photothermal filler to remotely and spatially control the shape recovery of thermal-sensitive shape memory polymers (SMPs), while its introduction (1 wt%) had little influence on the thermal and mechanical properties of the polymer matrixes. Owing to their excellent NIR photothermal performance as well as a one-step synthetic preparation, these CMPs may be promising photothermal materials for practical applications.

The preparation of 3,4‐ethylenedioxy thiophene (EDOT)‐based conjugated microporous polymers by direct arylation polymerization and fluorescence‐sensing nitro‐aromatic compounds and iodine

“…The fluorescence intensities of the obtained EDOT‐based CMPs are higher than that of the corresponding building blocks. These redshifts and stronger fluorescence properties might be caused by the extended conjugated networks and the sequestration effect of the cross‐linked networks preventing the aggregation‐induced fluorescence quenching 55–57 …”

“…These values are close to the K SV values of other EDOT‐based POPs (Table S5). The limits of detection (LODs) were calculated according to the following formula: LOD = 3 s/slope (mol L −1 ) (s is the standard deviation of the slope at the linear fit) 57 . Their LODs based on the generalized three times standard deviation of measurements of the blank signals of the EDOT‐based CMPs' solutions are 4.57 × 10 −12 , 1.12 × 10 −8 , 4.37 × 10 −11 , and 7.52 × 10 −10 mol L −1 , respectively, which is also comparable to other reported porous materials (Table S5).…”

“…These redshifts and stronger fluorescence properties might be caused by the extended conjugated networks and the sequestration effect of the cross-linked networks preventing the aggregation-induced fluorescence quenching. [55][56][57] The fluorescence performances of the EDOT-based CMPs (2 mg) were also appraised in some solvents (2 mL), for instance, acetonitrile (ACN), acetone, 1,4-dioxane (DOX), THF, N,N-dimethylformamide (DMF), chloroform, and EtOH. The EDOT-based CMPs can be dispersed equably in the above solvents and exhibit strong fluorescence emission in some solvents (Figure 4).…”

Processable Conjugated Microporous Polymer Gels and Monoliths: Fundamentals and Versatile Applications

“…Especially, the π-conjugation effect of conjugated groups in CMP gel is different from ordinary polymer gel. For these highly conjugated porous gel networks, the π-conjugation effect on the backbone of polymerization coupled with mass transfer in porous systems leads to many unique properties, including fast electron transport and highly efficient matter exchange, which promotes their applications in energy storage, ,, light-energy conversion, , and electrochemiluminescence. , …”

Macroscale Conjugated Microporous Polymers: Controlling Versatile Functionalities Over Several Dimensions

“…Jiang et al [31] used a carbazole derivative, triindolocarbazole (TCB), to synthesize a TCB-CMP that exhibits blue luminescence and could be used to detect arenes upon exposure to their vapors. Thereafter, the CMP family has been largely developed and utilized in a plethora of fields including light emitters, [32] energy storage, [33,34] catalysis, [35] gas storage/separations, [36] chemosensors, [37,38] energy conversion, [39,40] biological applications, [41] etc.…”