Facile Construction of Metallo-supramolecular Poly(3-hexylthiophene)-block-Poly(ethylene oxide) Diblock Copolymers via Complementary Coordination and Their Self-Assembled Nanostructures

Abstract

Complementary coordination of two predesigned 2,2':6',2″-terpyridine-based ligands to a Zn ion led to the exclusive formation of a heteroleptic bis(terpyridine) complex under ambient conditions. This highly self-selective process was facilitated by 9-anthracenyl substituents at the 6,6″-positions of a terpyridine, which not only decelerated the formation rate of its homoleptic complex, but also provided π-stacking stabilization in the heteroleptic complex. Facile construction of metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-poly(ethylene oxide) (PEO) diblock copolymers was realized using the complementary ligand pair. The morphological studies of the amphiphilic block copolymers in solution were conducted by atomic force microscopy and transmission electron microscopy, indicating that the self-assembled core-shell morphology such as spherical and fibrillar nanostructures could be controlled by adjusting the rod-coil block ratios. The heteroleptic complexes residing at the junction between two polymer blocks could be readily dissociated by EDTA to afford the unshelled P3HT nanofiber networks, and restored by treatment of bifunctional Zn-terpyridine-capped PEO to redisperse the aggregates. The presented supramolecular methodology highlights the merits of complementary metal-ligand coordination, and offers a new approach to engineering nanostructures assembled from rod-coil block copolymers.

Amphiphilic acrylamide block copolymer: RAFT block copolymerization and monolayer behaviour

“…Controlling the nanoscale self-assembly of polymer materials is a key issue in various elds such as biomimetic materials [1][2][3][4][5] and exible electronics device science. [6][7][8][9][10] To achieve and improve control, both material synthesis and processing methodology have been developing synergistically, thereby providing molecular design and bottom-up approaches for the simple and precise control of nanostructures. The Langmuir-Blodgett (LB) technique is a notable example of nanoscale assembly using an air-water interface.…”

Early Metal Di(pyridyl) Pyrrolide Complexes with Second Coordination Sphere Arene−π Interactions: Ligand Binding and Ethylene Polymerization

“…16 Chan and co-workers also demonstrated that incorporation of both 2,6-dimethoxyphenyl, G , and anthracenyl, H , groups on to the terpy backbone can be used to selectively prepare the heteroligated complexes as a consequence of the favorable electronics of π-stacking in these cases. 17 Despite these and other 18 examples of arene-appended terpy ligands displaying favorable π–π interactions in the solid state, monoligated complexes, in the absence of additional ligands bearing extended π-systems, do not display parallel aryl substituents in the solid state 19 as a consequence of the central six-membered pyridine donor.…”

Metallo-supramolecular complexes from mPEG/PDPA diblock copolymers and their self-assembled strip nanosheets

“…[29][30][31][32] For this method, the polymer units containing ligand moieties (macroligands) are rst designed and synthesized, and the tailored units are then held together through the coordination with metal ions. 12,[14][15][16][17][18][19][20][21][22][23][24]30 Among ligand groups, 2,2 0 :6 0 ,2 00 -terpyridine (Tpy) moiety is widely introduced into polymer building blocks for synthesizing macroligands, 12,[14][15][16][17][18][19][20][21][22][23][28][29][30][31][32] because it is able to form stable Tpy-M-Tpy (M, metal ion) complexes with a wide range of metal ions such as Ni(II), Fe(II), Cu(II), Co(II), Zn(II), Cd(II) and Ru(II), [29][30][31][32][33][34] making the formed metallosupramolecular polymers have a well-dened architecture. [15][16][17][18][19][20][21]<...>…”

“…12,[14][15][16][17][18][19][20][21][22][23][24]30 Among ligand groups, 2,2 0 :6 0 ,2 00 -terpyridine (Tpy) moiety is widely introduced into polymer building blocks for synthesizing macroligands, 12,[14][15][16][17][18][19][20][21][22][23][28][29][30][31][32] because it is able to form stable Tpy-M-Tpy (M, metal ion) complexes with a wide range of metal ions such as Ni(II), Fe(II), Cu(II), Co(II), Zn(II), Cd(II) and Ru(II), [29][30][31][32][33][34] making the formed metallosupramolecular polymers have a well-dened architecture. [15][16][17][18][19][20][21][22][23]30 Among complex species, Tpy-Ni(II)-Tpy and Tpy-Ru(II)-Tpy types exhibit good stability in water. 14 U. S. Schubert et al have investigated synthesis and coordination selfassembly of Tpy-containing polymers extensively and indepth.…”