Self‐assembly of H‐bonded side‐chain and cross‐linking copolymers containing diblock‐copolymeric donors and single/double H‐bonded light‐emitting acceptors

Abstract

A series of diblock-copolymers were synthesized through anionic polymerization of styrene and tert-butyl methacrylate (tBuA) with different monomer ratios, and analogous block-copolymeric derivatives (PS-b-PAA)s with monofunctional carboxylic acid groups were obtained by further hydrolyzation as hydrogen-bonded (H-bonded) proton donors. Via H-bonded interaction, these diblock-coplymeric donors (PS-b-PAA)s were incorporated with luminescent mono-pyridyl/bis-pyridyl acceptors to form single/double H-bonded supramolecules, that is, H-bonded side-chain/crosslinking copolymers, respectively. The supramolecular architectures formed by donor polymers and light-emitting acceptors were influenced by the ratio of acid blocks in the diblock copolymeric donors and the type of single/double H-bonded light-emitting acceptors. Their thermal and luminescent properties can be adjusted by H-bonds, and more than 100 nm of red-shifted photoluminescence (PL) emissions were observed, which depend on the degrees of the H-bonding interactions. Self-assembled phenomena of amphiphilic dibolck copolymers and their H-bonded complexes were confirmed by TEM micrographs, and supramolecular microphase separation of spherical micelle-like morphology was demonstrated to affect the photophysical properties. Polymer light-emitting diode (PLED) devices containing H-bonded complexes showed electroluminescence (EL) emissions of 503-560 nm under turn-on voltages of 7.5-9.0 V, maximum power efficiencies of 0.23-0.37 cd/A (at 100 mA/cm 2 ), and maximum luminances of 318-519 cd/m 2 (around 25 V). V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: [4685][4686][4687][4688][4689][4690][4691][4692][4693][4694][4695][4696][4697][4698][4699][4700][4701][4702] 2009

Spacer‐length‐dependent association in polymers with multiple‐hydrogen‐bonded end groups

“…The solution was stirred for 12 h, and it was allowed to warm to room temperature (careful: do not to let the temperature become higher). The solution was transferred to a separatory funnel and washed with 1 M HCl (3Â 500 mL), saturated NaHCO 3 (3Â 500 mL) and brine (1Â 100 mL), after which the organic layer was dried with MgSO 4 Synthesis of 6-(3-(6-Methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexyl-bromopropanoate (6) To a solution of 2-(1-imidazolylcarbonylamino)-6-methyl-4-[1H]-pyrimidinone (0.39 g, 1.90 mmol) and TFA salt 5 (0.58 g, 1.6 mmol) in 10 mL CHCl 3 was added 1 mL of triethylamine (0.72 g, 7.2 mmol). Subsequently, the solution was stirred for 12 h at a temperature of 45 C after which the solution was cooled and 20 mL of CHCl 3 was added.…”

“…Subsequently, the solution was stirred for 12 h at a temperature of 45 C after which the solution was cooled and 20 mL of CHCl 3 was added. The organic phase was washed with aqueous 1 M HCl (4Â 100 mL), saturated NaHCO 3 (2Â 70 mL) and brine (1Â 100 mL) and dried with MgSO 4 Synthesis of UPy End-Functional Poly(n-butyl acrylate), P(nBA) n -C 6 -UPy (2) n-Butyl acrylate (nBA, 3.00 g, 23.4 mmol), UPy initiator 6 (34.7 mg, 0.23 mmol), PMDETA (81 mg, 0.47 mmol) were combined in a Schlenk flask and subjected to three freezepump-thaw cycles. CuBr (12 mg, 0.24 mmol) was added under flowing nitrogen, and the flask was evacuated and backfilled with nitrogen twice.…”

“…[1][2][3][4] Theoretical work has shown that the domain size and morphology of the phase-separated structures critically depend on the strength of the interpolymer noncovalent interactions. [5][6][7][8][9][10] To achieve these attractive enthalpic interpolymer interactions, end-functionalized homopolymers have been prepared with functional groups capable of noncovalent assembly such as hydrogen bonding, [11][12][13][14][15][16][17][18][19][20] ionic, 21 transition-metal, 22,23 host-guest, [24][25][26] and fluorophilic 27 interactions.…”

“…KEYWORDS: atom transfer radical polymerization (ATRP); diffusion-ordered spectroscopy; hydrogen bonding; supramolecular diblock copolymers INTRODUCTION The combination of supramolecular chemistry and the controlled phase separation of diblock copolymers can result in a wealth of nanoscale morphologies with applications ranging from semiconductor integrated circuit design to the development of subnanometer porous films for separation processes. [1][2][3][4] Theoretical work has shown that the domain size and morphology of the phase-separated structures critically depend on the strength of the interpolymer noncovalent interactions.…”

“…KEYWORDS: atom transfer radical polymerization (ATRP); diffusion-ordered spectroscopy; hydrogen bonding; supramolecular diblock copolymers INTRODUCTION The combination of supramolecular chemistry and the controlled phase separation of diblock copolymers can result in a wealth of nanoscale morphologies with applications ranging from semiconductor integrated circuit design to the development of subnanometer porous films for separation processes. [1][2][3][4] Theoretical work has shown that the domain size and morphology of the phase-separated structures critically depend on the strength of the interpolymer noncovalent interactions.5-10 To achieve these attractive enthalpic interpolymer interactions, end-functionalized homopolymers have been prepared with functional groups capable of noncovalent assembly such as hydrogen bonding, [11][12][13][14][15][16][17][18][19][20] ionic, 21 transition-metal, 22,23 host-guest, 24-26 and fluorophilic 27 interactions. Typically, these functional groups are attached to a homopolymer via a short, aliphatic spacer.…”