The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic diazafluorene-containing substrates (A_mB_n) with crescent shapes into Drawing Hands grids (DHGs). The meso-selectivity reaches 75.6% diastereomeric excess (de) during the gridization of A₁B₁-type substrates and maintains ~80% de during the polygridization of A₂B₂-type monomers. Such stereocontrol originates from the centrosymmetric molecular packing of two charge-delocalized superelectrophiles with synergistically π–π stacking attractions and coulombic repulsions. As meso-stereoregular structures show 20∼30 nm in length, the rigid ring/chain-alternating polygrids have a Mark–Houwink exponent of 1.651 and a molecular weight (M) dependence of the hydrodynamic radius R_h ∼ M^1.13. Via the simulation of chain collapse, meso-configured polygridarenes still adopt rod-like conformations that facilitate the high rigidity of organic nanopolymers, distinguished from toroid backbones of rac-type polygrids.

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.

Gridization is an emerging molecular integration technology that enables the creation of multifunctional organic semiconductors through precise linkages. While Friedel-Crafts gridization of fluorenols is potent, direct linkage among fluorene molecules poses a challenge. Herein, we report an achiral Pd-PPh₃-cataylized diastereoselective (>99:1 d.r.) gridization based on the C-H-activation of fluorene to give dimeric and trimeric windmill-type nanogrids (DWGs and TWGs). These non-conjugated stereo-nanogrids showcase intramolecular multiple H^…H interactions with a low field shift to 8.51 ppm and circularly polarized luminescence with high luminescent dissymmetry factors (|g_PL | = 0.012). Significantly, the nondoped organic light-emitting diodes (OLEDs) utilizing cis-trans-TWG1 emitter present an ultraviolet electroluminescent peak at ~386 nm (CIE: 0.17, 0.04) with a maximum external quantum efficiency of 4.17%, marking the highest record among nondoped ultraviolet OLEDs based on hydrocarbon compounds and the pioneering ultraviolet OLEDs based on macrocycles. These nanohydrocarbon offer potential nanoscafflolds for ultraviolet light-emitting optoelectronic applications.

Diamond-type nanogrids (DGs), can helically expand to form spiro-linked polymers. Herein, we designed and synthesized two types of DGs, DGs-1 (A ₁ B ₁ mode) in 44–50% yields, and DGs-2 (A ₂ + B ₂ mode) in 64% yield.