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Linear Coordination Polymer Synthesis from Bis-Catechol Functionalized RAFT Polymers.
Macromolecular Rapid Communications ( IF 4.6 ) Pub Date : 2020-08-05 , DOI: 10.1002/marc.202000366
Reece W Lewis 1, 2 , Nino Malic 2 , Kei Saito 3 , Neil R Cameron 1, 4 , Richard A Evans 2
Affiliation  

Catechol‐Fe(III) complexes contain some of the strongest known metal‐chelate coordination bonds. Despite this, they have until now not been utilized in (polymeric linker) linear coordination polymer (LCP) synthesis. With the view of generating catechol end‐functional polymers, a new, symmetrical bis‐catechol functionalized trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agent is synthesized (CatDMAT). Acrylamide (AM) and dimethylacrylamide (DMA) polymerizations are conducted with CatDMAT using direct photoactivation RAFT polymerization to yield bis‐catechol end‐functionalized homo‐ and block‐copolymers of molecular weight 10–15 kDa. Catechol‐Fe(III) LCPs are successfully formed from the telechelic catechol polymers by bis‐complexation to Fe(III). The tetrahedral bis‐complex is detected by UV–vis spectroscopy (λmax = 570 nm), while increases in relative viscosity and Mn,GPC over their respective uncomplexed polymers confirm the occurrence of supramolecular polymerization. The catechol‐LCPs are shown to undergo oxidation and crosslinking in aqueous solution after 24 h.

中文翻译:

由双邻苯二酚官能化的RAFT聚合物合成线性配位聚合物。

邻苯二酚-铁(III)配合物包含一些已知最强的金属-螯合物配位键。尽管如此,到目前为止,它们还没有用于(聚合物接头)线性配位聚合物(LCP)合成中。为了生成邻苯二酚末端官能聚合物,合成了一种新型的对称双邻苯二酚官能化的三硫代碳酸酯可逆加成断裂链转移(RAFT)剂(CatDMAT)。使用直接光活化RAFT聚合,通过CatDMAT进行丙烯酰胺(AM)和二甲基丙烯酰胺(DMA)聚合,以生成分子量为10-15 kDa的双邻苯二酚末端官能化的均聚物和嵌段共聚物。邻苯二酚儿茶酚聚合物通过双络合成Fe(III)成功地形成了邻苯二酚-Fe(III)LCP。四面体双络合物通过紫外可见光谱法(λ最大值 = 570 nm),而相对粘度和M n,GPC的增加分别超过其各自的未络合聚合物,这证实了超分子聚合的发生。已显示24小时后,邻苯二酚LCP在水溶液中发生氧化和交联。
更新日期:2020-09-22
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