Synthesis and hierarchical self-assembly of luminescent platinum(ii)-containing telechelic metallopolymers

Abstract

Telechelic polymers that contain a central polymer chain and two metal complex terminals would represent a novel class of functional metallopolymers. In this work, a series of telechelic polystyrenes end-difunctionalized...

Synthesis of Platinum(II)-Containing Block Copolymers: Luminescence Enhancement and Controllable Self-Assembly

“…1,2,28−41 They resemble, in size, π-conjugated macrocycles, 42,43 and oligomers 44−46 that are commonly utilized to create rod−coil diblock copolymers and their functional nanoassemblies. Accordingly, the nanosized metal−ligand complexes such as zinc(II), 1,2,28−30 lanthanide(III), 1,2,28−30 and platinum(II) complexes 31−41 can be recognized as an individual, rigid building unit to microphase separate polymeric segments, leading to the creation of micelle-like aggregates in solution [31][32][33][34][35]37,38 and ordered nanostructures in thin film. 39−41 The resulting nanoassemblies can be directly imaged by using transmission electron microscopy (TEM) without any other staining as a result of the higher electron density of metal−ligand complexes than polymeric segments.…”

“…39−41 The resulting nanoassemblies can be directly imaged by using transmission electron microscopy (TEM) without any other staining as a result of the higher electron density of metal−ligand complexes than polymeric segments. [28][29][30][31][32][33][34][35]37,38,47 As part of our program to study metal-containing polymers, we recently designed and synthesized a series of [Pt(bzimpy)-Cl] + -containing polymers. [31][32][33][34][35][36]40,41 The used polymeric segments include polystyrene (PS), 31−36 PEO, 40 and poly(εcaprolactone).…”

“…[28][29][30][31][32][33][34][35]37,38,47 As part of our program to study metal-containing polymers, we recently designed and synthesized a series of [Pt(bzimpy)-Cl] + -containing polymers. [31][32][33][34][35][36]40,41 The used polymeric segments include polystyrene (PS), 31−36 PEO, 40 and poly(εcaprolactone). 41 The [Pt(bzimpy)Cl] + complex is planar and has a molecular size of 1.2 × 1.0 nm 2 × 0.35 nm.…”

“…40,41 Their phosphorescence emissions and quantum yields are intensified significantly as a result of increasing Pt(II)•••Pt(II) and/or π−π stacking interactions. [31][32][33][34][35][36]40,41 Up to now, great effort has mainly focused on [Pt(bzimpy)Cl] + -containing homopolymers, while [Pt(bzimpy)Cl] + -containing diblock copolymers are rarely explored.…”

“…The metal–ligand complexes formed with 2,2′:6′,2″-terpyridine have been widely utilized as a supramolecular alternative to create metallosupramolecular block copolymers that share a typical molecular architecture with conventional block copolymers linked by covalent bonds. − Typically, the metallosupramolecular block copolymers of PEO–[M]–PS (PEO = poly­(ethylene oxide), PS = polystyrene, M = Ru II , Ni II , or Co III ) can self-assemble to generate micelle-like aggregates in selective solvents , and nanoporous thin films by breaking the metal–ligand coordination bonds and then removing the PEO block. − The note is that the metal–ligand complexes obtained with 2,2′:6′,2″-terpyridine or 2,6-bis­(benzimidazol-2′-yl)­pyridine (bzimpy) occupy sizes ranging from 1 to 3 nm. ,,− They resemble, in size, π-conjugated macrocycles, , and oligomers − that are commonly utilized to create rod–coil diblock copolymers and their functional nanoassemblies. Accordingly, the nanosized metal–ligand complexes such as zinc­(II), ,,− lanthanide­(III), ,,− and platinum­(II) complexes − can be recognized as an individual, rigid building unit to microphase separate polymeric segments, leading to the creation of micelle-like aggregates in solution − ,, and ordered nanostructures in thin film. − The resulting nanoassemblies can be directly imaged by using transmission electron microscopy (TEM) without any other staining as a result of the higher electron density of metal–ligand complexes than polymeric segments. −…”