Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure–property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure–property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure–property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm² V⁻¹ s⁻¹, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure–property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices.

The lower charge mobility of organic semiconductors relative to that of inorganic semiconductors is a thorny problem that still has not been resolved. Here, a new type of arrangement of grid-shaped organic semiconductors with extremely low values of internal reorganization energies (IREs) for both hole (0.056 eV) and electron (0.078 eV) transfer processes has been designed and investigated by density functional theory (DFT) calculations. The structural, thermodynamic and electronic properties of grid spirofluorene (GSF) consisting of four spirobifluorenes have been discussed thoroughly. Our analyses of these unique grid structures indicate that they possess a stringent structure and very weak ring strain energy, and may be easily synthesized in the laboratory. Interestingly, GSF1, GSF2, and GSF9 possess both small hole and lower electron transfer reorganization energies (<0.1 eV), which may originate from their rigid molecular structures. The large π conjugated system in which all of the frontier molecular orbitals are homogeneously delocalized over the entire molecules is another important characteristic of these GSFs. This work reveals that the gridization method is a novel strategy for obtaining materials with low hole and electron transfer reorganization energies.

High dielectric constants in organic semiconductors have been identified as a central challenge for the improvement in not only piezoelectric, pyroelectric, and ferroelectric effects but also photoelectric conversion efficiency in OPVs, carrier mobility in OFETs, and charge density in charge-trapping memories. Herein, we report an ultralong persistence length ( l p ≈ 41 nm) effect of spiro-fused organic nanopolymers on dielectric properties, together with excitonic and charge carrier behaviors. The state-of-the-art nanopolymers, namely, nanopolyspirogrids (NPSGs), are synthesized via the simple cross-scale Friedel-Crafts polygridization of A ₂ B ₂ -type nanomonomers. The high dielectric constant ( k = 8.43 ) of NPSG is firstly achieved by locking spiro-polygridization effect that results in the enhancement of dipole polarization. When doping into a polystyrene-based dielectric layer, such a high- k feature of NPSG increases the field-effect carrier mobility from 0.20 to 0.90 cm ² V ^-1 s ^-1 in pentacene OFET devices. Meanwhile, amorphous NPSG film exhibits an ultralow energy disorder (<50 meV) for an excellent zero-field hole mobility of 3.94 × 10 − 3 c m 2 V − 1 s − 1 , surpassing most of the amorphous π -conjugated polymers. Organic nanopolymers with high dielectric constants open a new way to break through the bottleneck of efficiency and multifunctionality in the blueprint of the fourth-generation semiconductors.

In situ self-assembly of semiconducting emitters into multilayer cracks is a significant solution-processing method to fabricate organic high- Q lasers. However, it is still difficult to realize from conventional conjugated polymers. Herein, we create the molecular super-hindrance-etching technology, based on the π-functional nanopolymer PG-Cz, to modulate multilayer cracks applied in organic single-component random lasers. Massive interface cracks are formed by promoting interchain disentanglement with the super-steric hindrance effect of π-interrupted main chains, and multilayer morphologies with photonic-crystal-like ordering are also generated simultaneously during the drop-casting method. Meanwhile, the enhancement of quantum yields on micrometer-thick films ( Φ = 40% to 50%) ensures high-efficient and ultrastable deep-blue emission. Furthermore, a deep-blue random lasing is achieved with narrow linewidths ~0.08 nm and high-quality factors Q ≈ 5,500 to 6,200. These findings will offer promising pathways of organic π-nanopolymers for the simplification of solution processes applied in lasing devices and wearable photonics.