Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-b-PS Diblock Copolymers

Tu, Tsung‐Han; Chan, Yi‐Tsu

doi:10.3390/polym12122842

Cited by 9 publications

(7 citation statements)

References 57 publications

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“…Likewise, Schmittel and co-workers have avoided the formation of homoleptic phenanthroline complexes by grafting bulky aryl groups at the 2,9-positions. , The resulting spatial hindrance avoids the complexation of two bulky ligands while still allowing heteroleptic complexes to form in combination with less sterically demanding ligands like terpyridine or unsubstituted phenanthroline. Heteroleptic complexes have also been widely used as static units for the construction of highly ordered complex supramolecular arrays − and as dynamic groups for the induction of structural rearrangements in molecular machines. − However, their application in the field of polymer science has been limited to recent reports on the formation of A–B-type block copolymers. − This is unfortunate as the incorporation of dynamic heteroleptic complexes not only defines new paradigms for designing smart polymeric materials but can also provide a new scale for the recognition of self-sorting mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

Ahmadi

Seiffert

2021

Macromolecules

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Heteroleptic complexes are widely employed in small-molecule supramolecular arrays for the construction of complex architectures or for inducing nanoscopic rearrangements upon application of external stimuli that change the coordination-geometry preference. Despite this potential, they are rarely employed in the development of metallo-supramolecular polymer networks; this is unfortunate as that strategy might actually provide a tool to build highly homogeneous model-type networks that could form a basis for both a myriad of elementary investigations on transient networks and for their use in rational soft-functional materials design. To close that gap, we mix aqueous solutions of terpyridine- and phenanthroline-functionalized tetra-arm poly(ethylene glycol) (tetraPEG) precursors right at the overlap concentration and form physical hydrogels by introducing various types of divalent transition metal ions. The formation of heteroleptic complexes is comprehended by the persistence of the network percolation at intermediate network compositions, as revealed by rheological measurements. Specifically, shear stress curves and the resulting relaxation time spectra demonstrate the emergence of a third relaxation mode, on top of those associated with homoleptic complexes, which is indicative of heteroleptic complexation. Spectroscopic analyses and DFT calculations suggest the possible formation of heteroleptic complexes with all studied metal ions, whereby their fraction and lifetime are traceable using rheological measurements in the case of networks formed by Co2+ ions. Moreover, employing over-stoichiometric Co2+-to-ligand ratios eventually results in the selective formation of heteroleptic complexes. These results not only suggest new paradigms for devising smart soft materials, but they also propose new dimensions for characterizing heteroleptic complexes.

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Section: Introductionmentioning

confidence: 99%

Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

Ahmadi

Seiffert

2021

Macromolecules

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“…In this context, 9-anthracenyl modifications showed excellent results by also introducing π−π stacking effects with the unfunctionalized terpyridine ligand, enabling the formation of supramolecular AB-type blockcopolymers. 34,35 Additionally, Py end-functionalized polymers can be used to form supramolecular block copolymers or AB 4 -star polymers with ZnPor moieties. 30 The complete orthogonality of both binding concepts 36 enables the selective binding of different polymer counterparts at the same time, resulting in a highly efficient synthesis of sophisticated polymeric architectures such as ABC-type miktoarm star polymers.…”

Section: Resultsmentioning

confidence: 99%

“…Terpyridine-based ligands functionalized with sterically demanding groups at the 6 and 6″ positions are able to form heteroleptic complexes with an unfunctionalized terpyridine spontaneously. In this context, 9-anthracenyl modifications showed excellent results by also introducing π–π stacking effects with the unfunctionalized terpyridine ligand, enabling the formation of supramolecular AB-type blockcopolymers. , Additionally, Py end-functionalized polymers can be used to form supramolecular block copolymers or AB 4 -star polymers with ZnPor moieties …”

Section: Resultsmentioning

confidence: 99%

One-Pot Synthesis of Miktoarm Star Polymers Based on Orthogonal Metal–Ligand Interactions

Bätz

Anufriev

Pai

et al. 2023

ACS Appl. Polym. Mater.

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Miktoarm star polymers are a particular type of branched polymers featuring a star-shaped architecture with arms based on different polymer types. Such materials exhibit unique thermal, mechanical, and selfassembly properties. Hence, this polymer class is of great interest in different research fields. So far, the synthesis of these entities can be rather challenging, particularly applying covalent strategies for linking of the different polymers. Thus, an approach for the synthesis of such polymer architectures is presented using orthogonal metal−ligand interactions to connect the different building blocks, resulting in a miktoarm topology. The obtained structures are investigated via diffusion-ordered nuclear magnetic resonance spectroscopy, by analytical ultracentrifugation and dynamic light scattering.

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“…All the polymers were synthesized according to the previously reported procedures. , Generally, the well-defined tpy-modified PSs (PS 85 and PS 161 ) were synthesized using an Fe(II)-bis(tpy) complex bearing an α-Bromoester as the metallo-initiator for the atom transfer radical polymerization of styrene. After decomplexation, the chain-end functionalized PSs with controllable molecular weights and low polydispersities ( D̵ = M w / M n ) were realized.…”

Section: Resultsmentioning

confidence: 99%

Metallo-Supramolecular Rod–Coil Block Copolymer Thin Films for Stretchable Organic Field Effect Transistor Application

Pai

et al. 2022

Macromolecules

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Herein, to decrease the synthetic burden of the rod− coil diblock copolymers, the coordination-driven self-assembly approach is utilized to readily construct a series of polystyrene (PS)-block-poly(3-hexylthiophene) (P3HT) copolymers with dynamic heteroleptic coordination bonds between the two blocks. In detail, the chain length of the PS is varied for a fixed P3HT chain length to produce block copolymers, namely, PS 85 −Zn−P3HT 187 (P1) and PS 161 −Zn−P3HT 187 (P2), with comparable electrical performance to that of homopolymer P3HT (P0) in the unstrained state, along with enhanced crack onset strain and much less reduced mobility under 25−100% strain. The ability to maintain the charge transport characteristics is due to the longer coil chain length and amorphous PS regions for the dissipation of strain energy. The organic field effect transistors of P2 with a longer PS segment show only a slight change in mobility from 5.48 × 10 −3 to 1.40 × 10 −3 cm 2 V −1 s −1 under 25−100% and maintain this mobility even after being subjected to 100 repeated stretching/releasing cycles at 50% strain. This proof-of-concept demonstration of the proposed molecular engineering approach based on the metallosupramolecular method provides a suitable route to the molecular design of stretchable polymer semiconductors with balanced mechanical and electrical behaviors.

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Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-b-PS Diblock Copolymers

Cited by 9 publications

References 57 publications

Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

One-Pot Synthesis of Miktoarm Star Polymers Based on Orthogonal Metal–Ligand Interactions

Metallo-Supramolecular Rod–Coil Block Copolymer Thin Films for Stretchable Organic Field Effect Transistor Application

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