Multiple Stimuli-Responsive and White-Light Emission of One-Pot Synthesized Block Copolymers Containing Poly(3-hexylthiophene) and Poly(triethyl glycol allene) Segments

Abstract

Conjugated block copolymers with tunable properties have attract considerable research interests in recent years. Herein, we report a series of novel block copolymers containing conjugated poly(3-hexylthiophene) (P3HT) and poly(triethyl glycol allene) (PTA) segments which were synthesized in one pot using nickel complex as a single catalyst via distinct polymerization mechanisms. Interestingly, the P3HT-b-PTA diblock copolymers exhibit excellent thermoresponsive properties in water, and the lower critical solution temperature (LCST) is dependent on polymer concentration and the block ratio. Moreover, the diblock copolymers showed pH-responsive properties in CHCl 3 with the emission color shuttled between orange and deep green upon the alternate additions of trifluoroacetic acid and triethylamine. Both P3HT-b-PTA and P3HT-b-PTA-b-P3HT block copolymers exhibit solvatochromism properties. The emission of the block copolymers can be facilely tuned through variation on solvents with the emission color spanned widely from red to blue. Very interestingly, white-light emission can be readily achieved from the P3HT-b-PTA-b-P3HT triblock copolymer in the mixture of THF and methanol with 1/3 volume ratio.

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

“…Such tight assembly may significantly reduce the conjugated length of coplanar P3HT,thus it showed ablue-light emission, similar to thiophene oligomers. [61,62] CDASA-induced CPL During the formation of single-handed helical micelles through CDASA, the chirality of helical PPI segment was transferred to the self-assembled P3HT block, which might trigger aC PL. To testify this hypothesis,t he excited-state chirality of single-handed helical micelles was analyzed by CPL spectroscopy.Whereas,very weak CPL was detected on the right-handed helical micelles of poly(1 20 -b-2L 50 )u pon excited at 365 nm in toluene/IPA( v/v = 4/6) as that of the induced white-light emission.…”

Glycosylated Cell‐Penetrating Poly(disulfide)s: Multifunctional Cellular Uptake at High Solubility

“…GPC Analysis of CPDs 7 confirmed a very low polydispersity of PDI = 1.03 ± 0.04 and a relatively short length with n = 19 monomers per polymer, resulting in an M w = 9.5 ± 1.2 kDa . The alkynated d ‐glucose 11 was obtained from d ‐glucose 12 by acid catalyzed glycosidation with alkyne 13 following reported procedures . Temporary benzoyl protection was necessary to isolate pure α anomer 11 ( Scheme ).…”

“…CPDs 14 – 16 were prepared in similarly high yield following the same procedure ( Scheme ). The necessary alkyne substrates 15 – 19 were readily accessible following literature procedures ( Figure , Scheme ) . The original CPDs 2 were prepared for comparison, following the reported procedures optimized to obtain polymers of comparable properties (PDI = 1.22 ± 0.15, n = 19, M w = 9.3 ± 1.4 kDa) …”

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

“…Block copolymerization of allene derivatives also can be conducted because of the stability of living π‐allylnickel end groups and the molecular weights of the corresponding block copolymers could be tuned by the feeding ratio . Moreover, block copolymers of allene derivatives with butadiene, isocyanides, or 3‐hexylthiophene have been synthesized by sequential feeding because all these monomers can also be polymerized with [( η 3 ‐allyl)NiOCOCF 3 ] 2 .…”