Luminescent (metallo-supramolecular) cross- linked lanthanide hydrogels from a btp (2,3-bis(1,2,3-triazol-4-yl)picolinamide) monomer give rise to strong Tb(III) and Eu(III) centred emissions
Luminescent (metallo-supramolecular) cross- linked lanthanide hydrogels from a btp (2,3-bis(1,2,3-triazol-4-yl)picolinamide) monomer give rise to strong Tb(III) and Eu(III) centred emissions
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DOI：
10.1039/d2qm00998f
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发表时间：
2023-01-24
影响因子：
7
通讯作者：
Gunnlaugsson, Thorfinnur
中科院分区：
文献类型：
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作者：
Hegarty, Isabel N.;Bradberry, Samuel J.;Gunnlaugsson, Thorfinnur
描述了2,3-二（1,2,3-三唑-4-酰基）吡啶酰胺（btp）配体2的发展，从胺1（也具有结构特征）具有甲基丙烯酰胺单元，促进了btp配体共聚合成聚合物水凝胶，使用2-羟乙基甲基丙烯酸酯（HEMA），甲基丙烯酸甲酯（MMA）和乙二醇二甲基丙烯酸酯（EGDMA），导致形成两种不同浓度的聚合物（作为聚合物薄膜）。分别为F1 （0.03 wt%）和F2 (0.3 wt%)，然后用这些聚合物与能与btp配体配合的镧系离子形成发光软材料；本文的重点是后一种聚合物显示出更强的发光。具有乙酰胺部分的非聚合配体3也被开发为模型化合物。我们还介绍了由前驱体1形成的软材料（超分子水凝胶），该材料被证明是热可逆形成的，并探讨了其形态和流变性能。我们还表明，在这种超分子凝胶中加入Tb（III）后，我们在离子与btp配体的配位上中断了软材料特征。虽然本文的重点是F2，但在这两种情况下，金属离子配位（通过这些离子溶液中的聚合物水化而实现）不仅会形成发光材料（已知Tb（III）在离子与btp配体配位时产生高度发光的绿色发射），而且还会在聚合物基体内瞬间形成金属介导的交联。在溶液中，以及在水凝胶内聚合后，2和3的光物理性质都呈现出来；在Tb（III）的情况下，导致形成肉眼清晰可见的绿色发光聚合物。同样地，我们证明在使用Eu（III）时，可以从聚合物F2中观察到红色发射。
The development of the 2,3-bis(1,2,3-triazol-4-yl)picolinamide (btp) ligand 2, from the amine 1 (which was also structurally characterised) possessing a methyacrylamide unit that facilitated the co-polymerisation of this btp ligand into polymeric hydrogels, using 2-hydroxyethyl methacrylate (HEMA), methylmethacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA), is described, resulting in the formation of two polymers with two different concentrations (cast as polymeric films), F1 (0.03 wt%) and F2 (0.3 wt%), respectively, These polymers were then used to form luminescent soft-materials using lanthanide ions, which can coordinate to the btp ligands; the focus herein on the latter polymer was shown to be more luminescent. The non-polymerisable ligand 3, possessing an acetamide moiety was also developed as a model compound. We also present the formation of a soft material (a supramolecular hydrogel) from the precursor 1, which was shown to be thermoreversibly formed, and its morphological and rheological properties were probed. We also show that upon addition of Tb(III), to this supramolecular gel, we have interrupted the soft-material features upon coordination of the ion to the btp ligands. While the focus herein is on the F2, in both cases the metal ion coordination (which was achieved upon hydration of the polymers in solutions of these ions) results not only in the formation of a luminescent material (Tb(III) is known to give rise to highly luminescent green emission upon coordination of the ion to btp ligands), but also in the instantaneous formation of metal mediated crosslinking within the polymeric matrix. The photophysical properties of both 2 and 3 are presented, both in solution, and as in the case of 2, after the polymerisation within the hydrogel; which in the case of Tb(III) results in the formation of green emitting polymers, clearly visible to the naked eye. Similarly, we demonstrate that upon using Eu(III), red emission is observed from polymer F2.