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Redox‐Triggered Folding of Self‐Assembled Coordination Polymers incorporating Viologen Units
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-07-27 , DOI: 10.1002/chem.201802088 Wathiq Sattar Abdul-Hassan 1, 2 , Denis Roux 3 , Christophe Bucher 4 , Saioa Cobo 1 , Florian Molton 1 , Eric Saint-Aman 1 , Guy Royal 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-07-27 , DOI: 10.1002/chem.201802088 Wathiq Sattar Abdul-Hassan 1, 2 , Denis Roux 3 , Christophe Bucher 4 , Saioa Cobo 1 , Florian Molton 1 , Eric Saint-Aman 1 , Guy Royal 1
Affiliation
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We report the study of stimuli‐responsive ZnII and FeII coordination polymers (MC34+ or MC24+ with M=Fe2+ or Zn2+). These soluble metallopolymers were formed spontaneously by reaction of an organic ligand (C34+ or C24+) with one molar equivalent of metal ions. The C34+ and C24+ ligands incorporate two chelating terpyridine groups bridged by a redox responsive hinge featuring two viologen units (viologen=N,N′‐dialkyl‐4,4′‐bipyridinium) linked either with propyl (C34+) or ethyl (C24+) chains. The viologen units in the polymer chains were reduced (1 e− per viologen group) either by bulk electrolysis or by visible‐light irradiation carried out in the presence of a photosensitizer. The 1 e− reduction of the viologen units in the MC24+ polymers induced a slight decrease in the viscosity of the solutions due to a modification of the overall charge carried by the metallopolymers. In strong contrast, reduction of coordination polymers involving propyl linkers (MC34+) led to a remarkable increase (≈+400 %) in observed viscosity. This reversible effect was attributed to a folding of the polymer chains triggered by π‐dimerization of the photo‐generated viologen cation radicals.
中文翻译：
含紫精单元的自组装配位聚合物的氧化还原触发折叠
我们报道了对刺激性反应的Zn II和Fe II配位聚合物（MC3 4+或MC2 4 +，M = Fe 2+或Zn 2+）的研究。这些可溶性金属聚合物是通过有机配体（C3 4+或C2 4+）与一摩尔当量的金属离子自发形成的。的C3 4+和C2 4+配体包括两个螯合三联吡啶基团桥连的通过氧化还原反应铰链具有两个紫精单元（紫精= Ñ，Ñ与丙基（C3 4+）或乙基（C2 4+）链连接的'-二烷基-4,4'-联吡啶鎓。在聚合物链中的紫精单位被降低（图1e -或者通过本体电解或通过可见光照射在光敏剂的存在下进行的每紫精组）。在图1e -还原紫精单元在MC2 4+由于由metallopolymers携带的总电荷的变形引起的溶液的粘度略有下降的聚合物。与之形成鲜明对比的是，还原涉及丙基接头的配位聚合物（MC3 4+）导致观察到的粘度显着增加（≈+ 400％）。这种可逆的作用归因于光生紫精阳离子自由基的π二聚化引发的聚合物链折叠。
更新日期：2018-07-27
中文翻译：
含紫精单元的自组装配位聚合物的氧化还原触发折叠
我们报道了对刺激性反应的Zn II和Fe II配位聚合物（MC3 4+或MC2 4 +，M = Fe 2+或Zn 2+）的研究。这些可溶性金属聚合物是通过有机配体（C3 4+或C2 4+）与一摩尔当量的金属离子自发形成的。的C3 4+和C2 4+配体包括两个螯合三联吡啶基团桥连的通过氧化还原反应铰链具有两个紫精单元（紫精= Ñ，Ñ与丙基（C3 4+）或乙基（C2 4+）链连接的'-二烷基-4,4'-联吡啶鎓。在聚合物链中的紫精单位被降低（图1e -或者通过本体电解或通过可见光照射在光敏剂的存在下进行的每紫精组）。在图1e -还原紫精单元在MC2 4+由于由metallopolymers携带的总电荷的变形引起的溶液的粘度略有下降的聚合物。与之形成鲜明对比的是，还原涉及丙基接头的配位聚合物（MC3 4+）导致观察到的粘度显着增加（≈+ 400％）。这种可逆的作用归因于光生紫精阳离子自由基的π二聚化引发的聚合物链折叠。
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