New series of AB₂‐type hyperbranched polytriazoles derived from the same polymeric intermediate: Different endcapping spacers with adjustable bulk and convenient syntheses via click chemistry under copper(I) catalysis

Abstract

In this article, according to the concept of “suitable isolation group,” six new AB2‐type polytriazoles containing azo‐chromophore moieties, derived from the same hyperbranched polymer intermediate, were successfully prepared through click reaction under copper(I) catalysis by modifying the synthetic route, in which different isolation groups in different size were introduced to the periphery of the hyperbranched polymers as end‐capping moieties. With the different end‐capping groups, these hyperbranched polymers, P1–P6, exhibited different solubility and processability; also, their nonlinear optical properties were modified accordingly, realizing the adjustment of the properties of hyperbranched polymers through the structural design. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A Series of Hyperbranched Polytriazoles Containing Perfluoroaromatic Rings from AB2‐Type Monomers: Convenient Syntheses by Click Chemistry under Copper(I) Catalysis and Enhanced Optical Nonlinearity

“…Fortunately, by modifying the synthetic procedure and adding the end‐capped groups, we have successfully prepared soluble azo‐chromophore‐containing AB 2 ‐type hyperbranched polytriazoles, HP‐NO 2 and HP‐SO 2 (see Chart S1 in the Supporting Information), which acted as new second‐order nonlinear optical (NLO) polymeric materials (one kind of materials with the promise of performance and cost improvements related to telecommunications, computing, embedded network sensing, THz wave generation and detection, and many other applications), with very exciting results such as enhanced NLO effects and simple syntheses 3a. To pursue the relationship between the structure and properties of this AB 2 ‐type hyperbranched polytriazoles and tackle the challenge in the NLO field (how to efficiently translate the large β values of the organic chromophores into high macroscopic NLO activities of polymers), we have introduced different sizes of the end‐capped groups to the periphery of the hyperbranched polymers as isolation moieties to adjust their solubility, processability, and NLO properties (see Chart S2 in the Supporting Information) 3b. However, with some improvement in their processability and structural adjustment,3b the NLO properties of these hyperbranched polymers were not very satisfying due to the reduced effective concentrations of the chromophore moieties as a result of a large amount of bulky groups in their periphery.…”

“…To pursue the relationship between the structure and properties of this AB 2 ‐type hyperbranched polytriazoles and tackle the challenge in the NLO field (how to efficiently translate the large β values of the organic chromophores into high macroscopic NLO activities of polymers), we have introduced different sizes of the end‐capped groups to the periphery of the hyperbranched polymers as isolation moieties to adjust their solubility, processability, and NLO properties (see Chart S2 in the Supporting Information) 3b. However, with some improvement in their processability and structural adjustment,3b the NLO properties of these hyperbranched polymers were not very satisfying due to the reduced effective concentrations of the chromophore moieties as a result of a large amount of bulky groups in their periphery. Thus, it was required to find some new approaches to improve the processability, solubility, and other properties of the resultant hyperbranched polymers, but without victimizing the possibly enhanced NLO effects.…”

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“…The overall pathway of the monomer synthesis was presented in Scheme . Usually, in the azo‐coupling reaction, diazonium hydrochloride was used as azo reagents, due to its high reaction activity 41–47. However, for the synthesis of chromophore S3 , there was no product yielded using this way, no matter we changed the different reaction conditions just like the concentration and pH values.…”

“…At present, this type of hyperbranched polymers have been intensively explored in many research fields, such as organic light‐emitting devices, liquid crystal devices, two‐photon absorption materials, supermolecular assembly, drug release, chemsensors, nanoscale catalysis, and so on,36–40 because of the efforts of scientists. Based on the unique properties of hyperbranched polymers, from 2006, our group have been prepared a series of new hyperbranched polymers as nonlinear optical (NLO) polymeric materials (one kind of material with the promise of performance and cost improvements related to telecommunications, computing, embedded network sensing, THz wave generation and detection, and many other applications) 41–47. The three‐dimensional (3D) spatial separation of the chromophore moieties in the hyperbranched polymers endows the polymers with favorable site isolation effect, which could minimize the strong intermolecular electrostatic interactions among chromophore moieties with high dipole moment, thus enhance the macroscopic optical nonlinearities of polymers, according to our previous work and the literatures 41–51…”

Asymmetric Tribranched Dyes: An Intramolecular Cosensitization Approach for Dye‐Sensitized Solar Cells

“…[18] A two-necked, round-bottomed flask equipped with a Dean-Stark apparatus was charged with diphenylamine (4.59 g, 27.10 mmol) and toluene (50 mL). [18] A two-necked, round-bottomed flask equipped with a Dean-Stark apparatus was charged with diphenylamine (4.59 g, 27.10 mmol) and toluene (50 mL).…”