Hyperbranched polymers (HPs) are highly branched three-dimensional (3D) macromolecules. Their globular and dendritic architectures endow them with unique structures and properties such as abundant functional groups, intramolecular cavities, low viscosity, and high solubility. HPs can be facilely synthesized via a one-pot polymerization of traditional small molecular monomers or emerging macromonomers. The great development in synthetic strategies, from click polymerization (i.e., copper-catalyzed azide–alkyne cycloaddition, metal-free azide–alkyne cycloaddition, strain-promoted azide–alkyne cycloaddition, thiol–ene/yne addition, Diels–Alder cycloaddition, Menschutkin reaction, and aza-Michael addition) to recently reported multicomponent reactions, gives rise to diverse HPs with desirable functional/hetero-functional groups and topologies such as segmented or sequential ones. Benefiting from tailorable structures and correspondingly special properties, the achieved HPs have been widely applied in various fields such as light-emitting materials, nanoscience and technology, supramolecular chemistry, biomaterials, hybrid materials and composites, coatings, adhesives, and modifiers. In this review, we mainly focus on the progress in the structural control, synthesis, functionalization, and potential applications of both conventional and segmented HPs reported over the last decade.

Hyperbranched polymers: advances from synthesis to applications

As one kind of important functional material, those with advanced optical, electrical and magnetic characteristics have attracted increasing attention due to their essential and irreplaceable role in the daily life of humans. In particular, optical, electrical and magnetic hyperbranched polymers (HBPs) exhibit some unique properties, partially derived from their highly branched topological structures. This review summarizes the recent progress in the field of functional HBPs and their application in optics, electronics and magnetics, including light-emitting polymers, nonlinear optical materials, chemosensors, solar cells, magnetic materials, etc., and also gives some outlooks for further exploration in this field at the end of this paper.

Functional hyperbranched polymers with advanced optical, electrical and magnetic properties.

Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics

The bidentate ligand 1,1’-bis(diphenylphosphino)ferrocene (dppf) is a widely used component in catalytic systems and its role in this capacity has been expertly reviewed elsewhere. The focus of this Perspective is the increasing use of dppf in the synthesis and matrix of 21st century materials. The ferrocene core imparts fine control to catalytic C–C and C–X coupling reactions used to manufacture a range of functional macromolecules from tailored dyes and OLED components to precisely engineered conducting polymers and thermoplastics. This ligand's limited flexibility resembles a ball and socket joint with simultaneous rotation and constrained perpendicular freedom. This uniquely restricted range of movement stabilizes a diverse array of ground and transition states for these important transition metal catalysed coupling reactions. It may also contribute desirable mechanical or electronic functionality as a bridging or chelating component in a coordination array, metallocycle or larger supramolecular assembly. The ferrocene offers steric bulk and crystallinity to these materials aiding chemical stability and ease of handing. It's oxidizability assists characterization and may be tailored to provide or complement photo- or electroactivity. Dppf containing materials have been designed with diverse functions from cooperative luminescence to host–guest complexation. It is likely that this ubiquitous lab companion will increasingly find its way into the fabric or processing of future functional molecular materials.

1,1’-Bis(diphenylphosphino)ferrocene in functional molecular materials

Fusing three perylenebisimide branches and a truxene core into a star-shaped chromophore with strong two-photon excited fluorescence and high photostability.

A series of novel hyperbranched ladder-type poly(p-phenylene)s containing truxene units have been prepared through the Pd(0)-catalyzed Suzuki polymerization with an “A2 + B3” or “A2 + B2+ B3” approach. The polymers with different linear length show pure blue light emission from 417 to 465 nm. All the ladder-type polymers exhibit well-resolved absorption and emission spectra and small Stokes shifts in both solutions and thin films, which are the characteristics of full ladder-type poly(p-phenylene)s. The three-dimensional structures make the materials soluble in common organic solvents and able to form quality amorphous films, leading to polymer light-emitting diodes (PLEDs) with improved stability and efficiency.

Pure Blue-Light-Emitting Materials: Hyperbranched Ladder-Type Poly( p -phenylene)s Containing Truxene Units

The novel inimer-containing fluorene units was successfully synthesized and characterized. Hyperbranched homopolymer and copolymers with methyl methacrylate (MMA) were prepared by the novel inimer via atom transfer radical polymerization where CuBr/1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) were used as catalyst. The copolymerization of inimer and MMA was performed under different ratio of the initial inimer/MMA and the inimer acted as not only the branched point (BP) but also the functional groups which emit blue light. The number-average molecular weight (M
 n) and polydispersity index (PDI) of polymers are in the ranges (3.6–18.4) × 103 and (1.3–2.8), respectively. Thermal gravimetric analysis (TGA) results showed all polymers had good thermal stabilities. The number of the inimers acted as branched point in the copolymer backbone is estimated by 1H NMR spectra and UV–Vis absorption spectra.

Synthesis and characterization of the novel inimer-containing fluorene units and preparation of blue light-emitting polymers

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Pure Blue-Light-Emitting Materials: Hyperbranched Ladder-Type Poly( p -phenylene)s Containing Truxene Units

Synthesis and characterization of the novel inimer-containing fluorene units and preparation of blue light-emitting polymers