Metallosupramolecular polymers

Schubert, U.S., Newkome, G.R., and Manners, I. 2006. Metal-Containing and Metallosupramolecular Polymers and Materials. Oxford University Press, New York. 

Schubert US, Eschbaumer C. Macromolecules containing bipyridine and terpyridine metal complexes towards metallosupramolecular polymers. Angew Chem Int Ed 2002 41 2892-2926. 

Chow C-F, Fuji S, Lehn J-M. Metallodynamers neutral dynamic metallosupramolecular polymers displaying transformation of mechanical and optical properties on constitutional exchange. Angew Chem Int Ed 2007 46 5007 -5010. 

Schubert US, Newkome GR, Manners I. Metal-containing and metallosupramolecular polymers and materials. Washington (DC) American Chemical Society 2006. 

Fig. 16 Mechanochemical evolution of metallosupramolecular polymers generated by (a) combination of an Eu(III) salt and a telechelic poly(ethylene-co-butylene) with 2,6-bis(l- -methylbenzimidazolyl)pyridine ligands at the termini counterions are omitted for clarity, (b) Reversible dissociation upon ultrasonication (i) irreversible metal exchange with Fe(II) ions as a result of (ii) ultrasonication or (Hi) other mechanical forces, (c) Dipicolinic acid ligands bind strongly to Eu(III) and the supramolecular network cannot easily be disassembled under mechanical stress. Reproduced with permission from [88]. Copyright 2014 American Chemical Society...

Balkenende DWR, Coulibaly S, Balog S, Simtm YC, Fiore GL, Weder C (2014) Mechanochemistry with metallosupramolecular polymers. J Am Chem Soc 136 10493-10498... 

Fig. 19 Mechanism and synthesis of photohealable metallosupramolecular polymers, (a) Proposed optical healing of a metallosupramolecular, phase separated network, (b) Synthesis of macromonomer 3 and polymerizatiMi by addition of Zn(NTf2)2. DEAD, diethyl azodicarboxylate. Reproduced with ptamission from 75]...

The self-assembly polymerization of ditopic monomers via metal-ligand binding is an easy route for the preparation of metallosupramolecular polymers [52]. 

In contrast to other metallosupramolecular polymers, where the nature of the metal salt plays a critical role, only minor property differences were observed for the materials studied here. The properties of the supramolecular poly(p-xylylene)s appear to be primarily governed by the crystalline nature of the telechelic oligomer [52]. 

Figure 7 Structure of Zn(II)-based metallosupramolecular polymer and the proposed multiblock-like phase segregation present in the solid state. The images highlight the elastic nature of the metallosupramolecular polymer. (Reproduced from Ref. 29. American Chemical Society, 2009.)...

Pal RR, Higuchi M, Negishi Y, Tsukuda T, Kurth DG (2010) Fluorescent Fe(II) metallosupramolecular polymers metal-ion-directed self-assembly of new bisterpyridines containing triethylene glycol chains. Polym J 42 336-341. doi 10.1038/pj.2010.3... 

Stenclova P, Vitvarova T, Svoboda J, Vohlidal J (2013) Synthesis and photophysical properties of alpha-omega-bis(terpyridyl)-oligothiophenes and their metallosupramolecular polymers. In ref. [18], 325... 

Like dynamic polymers in general, those of covalent type present specific properties that non-reversible polymers do not possess. They have been illustrated for instance in degradable green polymers based on imine connections [72], in polymer blending [73], in the modification of mechanical [74] and optical [75] properties. Metallosupramolecular polymers are also able to undergo dynamic modification of their mechanical and optical properties, as shown in Fig. 5 [53-55]. 

Whittell GR, Hager MD, Schubert US, Manners 1 (2011) Nature Mater. Functional Soft materials from metallopolymers and metallosupramolecular polymers 10 176-188... 

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