Complexation of Terpyridine‐Containing Dextrans: Toward Water‐Soluble Supramolecular Structures

Wild, Andreas; Hornig, Stephanie; Schlütter, Florian; Vitz, Jürgen; Friebe, Christian; Hager, Martin D.; Winter, Andreas; Schubert, Ulrich S.

doi:10.1002/marc.201000010

Cited by 11 publications

(4 citation statements)

References 27 publications

(37 reference statements)

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“…此外, 聚合物良好的机械性能和加工性能的引入极大地拓宽了双三联吡啶钌配合物的应用范围. [70,76,85,[187][188][189][190][191][192][193] 、瓶刷状聚合物 [62,194] 、树枝状大分子 [195][196][197][198][199][200] 、环状聚合物 [201] 和交联聚合物 [71][72]74] 等.…”

Section: 聚合物型双三联吡啶钌配合物unclassified

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★

Li,

Luo,

Chen

et al. 2023

Acta Chimica Sinica

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Over the past decades, thanks to the excellent directivity and stability of coordination bond between terpyridine and ruthenium ions, a large number of bis(terpyridine)-ruthenium(II) complexes have been constructed and reported through three synthetic strategies, i.e., direct coordination assembly, stepwise coordination assembly and post-assembly modification. Moreover, due to the unique photoelectric properties of bis(terpyridine)-ruthenium(II) complexes, these structures have shown great promise for applications in photothermal conversion, photovoltaic materials, electronic memory and anion exchange membranes. Therefore, this review summarizes the research progress of bis(terpyridine)-ruthenium(II) complexes with particular focus on small molecules, discrete supramolecules and polymers. Furthermore, current challenges and opportunities are briefly discussed. Keywords complex compound; terpyridine; ruthenium complex; coordination supramolecule; metallopolymer 1 引言由金属中心和配体通过配位键连接而成的配位化合物(简称配合物)在生命体 [1] 和现代工业生产 [2] 中均发挥着不可替代的作用, 诸如发挥光合作用的叶绿素 [3] 和输送氧气的血红蛋白 [4] , 以及在催化 [5][6][7][8][9][10][11][12][13][14] 、发光材料 [15][16][17][18][19][20][21] 、刺激响应性材料 [22][23][24][25][26] 、客体分子储存和分离 [27][28][29][30] 、离子识别 [31][32][33] 、传感器 [34][35] 、生物医疗 [36][37][38][39][40][41] 、导电和磁性材料 [42][43] 和量子计算 [44] 等领域呈现广泛应用的合成结构等. 理论上, 绝大多数过渡金属和镧系金属都可以作为配位键的金属中心, 配体则一般需要含有能够提供孤对电子的元素, 例如卡宾类、腈类、胺类、席夫碱类、吡啶类、醚类、酮类和膦类等 [45][46] . 基于此, 配合物的稳定性(即配位键强度)可以通过改变金属中心和配位元素的种类以及配位基团上配位元素的数量进行调节, 譬如吡啶、联吡啶和三联吡啶基团中随着氮原子数量的增多配位能力增强 [45][46][47] .除了上述三个氮原子集成的多齿配体特征外, 具有强给电子能力的三联吡啶基团在配位之前因氮原子上的孤对电子相互排斥, 结构中的三个吡啶环以反式构象存在, 而配位之后呈现为刚性平面顺式构象(图 1), 可与金属中心产生良好的共轭, 进一步增强了三联吡啶的配位能力 [11,48] . 因此, 三联吡啶(TPY)可与多种金属中心 (M)配位形成六配位八面体结构的双三联吡啶金属配合物＜TPY-M-TPY＞, 这些金属中心包括锰 Mn(II)、铁 Fe(II)、钴 Co(II)、镍 Ni(II)、铜 Cu(II)、锌 Zn(II)、镉

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Section: 聚合物型双三联吡啶钌配合物unclassified

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★

Li,

Luo,

Chen

et al. 2023

Acta Chimica Sinica

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“…At high concentrations, the polymer networks behaved as viscoelastic materials that were thermoreversible 16. Schubert and coworkers17 prepared tpy‐containing dextrans that form assemblies in the presence of Fe(II) or Ru(II) ions. Depending on the degree of tpy functionalization, a shift from intermolecular to intramolecular crosslinking was observed.…”

Section: Introductionmentioning

confidence: 99%

Poly(ethylene glycol)–poly(L‐lactide) star block copolymer hydrogels crosslinked by metal–ligand coordination

Buwalda

Dijkstra

Feijén

2012

J. Polym. Sci. A Polym. Chem.

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The aqueous solution behavior and thermoreversible gelation properties of pyridine‐end‐functionalized poly(ethylene glycol)–poly(L‐lactide) (PEG–(PLLA)8–py) star block copolymers in the presence of coordinating transition metal ions were studied. In aqueous solutions, the macromonomers self‐assembled into micelles and micellar aggregates at low concentrations and formed physically crosslinked, thermoreversible hydrogels above a critical gel concentration (CGC) of 8% w/v. In the presence of transition metal ions like Cu(II), Co(II), or Mn(II), the aggregate dimensions increased. Above the CGC, the gel–sol transition shifted to higher temperatures due to the formation of additional crosslinks from intermolecular coordination complexes between metal ions and pyridine ligands. Furthermore, as an example, PEG–(PLLA)8–py hydrogels stabilized by Mn(II)–pyridine coordination complexes were more resistant against degradation/dissolution when placed in phosphate buffered saline at 37 °C when compared with hydrogels prepared in water. Importantly, the stabilizing effect of metal–ligand coordination was noticeable at very low Cu(II) concentrations, which have been reported to be noncytotoxic for fibroblasts in vitro. These novel PEG–(PLLA)8–py metallo‐hydrogels, which are the first systems to combine metal–ligand coordination with the advantageous properties of PEG–PLLA copolymer hydrogels, are appealing materials that may find use in biomedical as well as environmental applications like the removal of heavy metal ions from waste streams. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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“…Similarly, polymers containing 2,2′:6′,2″‐terpyridine have also been synthesized by a number of research groups. In a series of article,5, 6, 9, 11, 13–15 Schubert and coworkers have prepared a number of well‐defined macromolecular polymeric ligands containing terpyridines end groups bearing different polymeric spacers with different properties 5. They have employed a Williamson type etherification approach for the reaction between 4′‐chloro‐2,2′:6′,2″‐terpyridine with a number of well‐defined mono‐ and bis ‐hydroxy functionalized polymers; the resulting terpyridine functionalized polymers could be considered as key candidates for the preparation metallo‐supramolecular polymers via metallo‐terpyridine complexation.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, They have functionalized dextran with 6‐(2,2′:6′,2″‐terpyridin‐4′‐yloxy)‐hexanoic acid using two different ratios of terpyridine to dextran, leading to terpyridine‐functionalized dextran esters possessing different degrees of substitution. They studied the “intra‐ and intermolecular″ complexation behavior of both functionalized biopolymers using Fe(II) metal ions as well as activated Ru(III) complexes and succeeded in obtaining water soluble comb‐polymer when using a PEG‐ functionalized terpyridine Ru(II) moiety for complexation 13. Moreover, the same research group described the synthesis and characterization of four metallo‐polymers containing either Zn(II) or Ru(II) ions in the main chain and were also able to produce the first photovoltaic devices out of these materials 14.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and adsorption properties, toward some heavy metal ions, of a new polystyrene‐based terpyridine polymer

Saadeh

Shairah

Charef

et al. 2011

J of Applied Polymer Sci

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A novel polymeric ligand having 2,2 0 :6 0 ,2 00 -terpyridine as pendant group was prepared through a Williamson type etherification approach for the reaction between 4 0 -hydroxy-2,2 0 : 6 0 ,2 00 -terpyridine and the commercially available 4-chloromethyl polystyrene. The chelating properties of the new polymer toward the divalent metal ions (Cu 2þ , Zn 2þ , Ni 2þ , and Pb 2þ ) in aqueous solutions was studied by a batch equilibration technique as a function of contact time, pH, mass of resin, and concentration of metal ions. The amount of metal-ion uptake of the polymer was determined by using atomic absorption spectrometry. Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Pb 2þ and that the metal-ion uptake follows the order: Pb 2þ > Cu 2þ > Zn 2þ > Ni 2þ . The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed.

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Complexation of Terpyridine‐Containing Dextrans: Toward Water‐Soluble Supramolecular Structures

Cited by 11 publications

References 27 publications

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★

Poly(ethylene glycol)–poly(L‐lactide) star block copolymer hydrogels crosslinked by metal–ligand coordination

Synthesis and adsorption properties, toward some heavy metal ions, of a new polystyrene‐based terpyridine polymer

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Complexation of Terpyridine‐Containing Dextrans: Toward Water‐Soluble Supramolecular Structures

Cited by 11 publications

References 27 publications

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes★

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes★

Poly(ethylene glycol)–poly(L‐lactide) star block copolymer hydrogels crosslinked by metal–ligand coordination

Synthesis and adsorption properties, toward some heavy metal ions, of a new polystyrene‐based terpyridine polymer

Contact Info

Product

Resources

About

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★

Research Progress of Bis(terpyridine)-Ruthenium(II) Complexes^★