We have designed novel macromolecular coordination ligands (MCLs) by conjugation of thermoresponsive polymers based on poly(N-isopropylacrylamide) (_n around 3 to 25 kg mol⁻¹) with 1,2,4-triazole coordination sites. These triazole units were integrated into two fundamentally different MCL architectures via reversible addition–fragmentation chain transfer polymerization following two synthetic strategies: (I) The customized chain transfer agent 1-{[3-(4H-1,2,4-triazol-4-yl)propyl]amino}-2-methyl-1-oxopropan-2-yl dodecyl carbonotrithioate (DMP-APTRZ) was employed for hemi-telechelic MCLs with a single triazole end group. (II) A tailored comonomer N-[3-(4H-1,2,4-triazol-4-yl)propyl]methacrylamide (APTRZMAAm) provides access to multidentate MCLs with a controllable number of triazole side groups along the polymer backbone. The thermally controlled variation of the MCL volume demand in aqueous solution was exploited for reversible aggregate formation upon Fe²⁺ complexation. Thermal response was studied via UV/Vis turbidity measurements, aggregate dimensions were determined via DLS, while the aggregate morphology was analyzed via customized TEM.

中文翻译：

---

作为大分子配位体的热响应聚合物：水溶液中热诱导聚集的络合依赖性

我们通过将基于聚（N-异丙基丙烯酰胺）（_n约 3 至 25 kg mol ^-1）的热敏聚合物与 1,2,4-三唑配位位点共轭，设计了新型大分子配位配体 (MCL) 。这些三唑单元按照两种合成策略通过可逆加成-断裂链转移聚合整合到两种根本不同的 MCL 结构中：（I）定制的链转移剂 1-{[3-(4 H -1,2,4-triazol- 4-基）丙基]氨基}-2-甲基-1-氧代丙-2-基十二烷基三硫代碳酸酯（DMP-APTRZ）用于具有单个三唑端基的半遥爪MCL。(II) 定制的共聚单体N -[3-(4 H-1,2,4-三唑-4-基)丙基]甲基丙烯酰胺 (APTRZMAAm) 提供了获得多齿 MCL 的途径，该 MCL 沿聚合物主链具有可控数量的三唑侧基。水溶液中 MCL 体积需求的热控制变化被用于在 Fe ²⁺络合时形成可逆的聚集体。通过UV/Vis 浊度测量研究热响应，通过DLS确定聚集体尺寸，而通过定制 TEM分析聚集体形态。