Suppressed excitonic effects enable high mobility, high-yield photoconductivity in a two-dimensional polymer crystal with axial pyridine coordination

TL;DR

This study demonstrates that axial pyridine coordination in a 2D polymer crystal significantly reduces excitonic effects, enabling high mobility and efficient photoconductivity comparable to inorganic materials.

Contribution

Introducing pyridine ligands to a 2D polymer crystal transforms stacking and electronic properties, overcoming excitonic limitations for improved charge transport.

Findings

Achieved room-temperature mobility approaching 500 cm^2 V^-1 s^-1.

Suppressed exciton binding energy below thermal energy.

Photoconductivity exceeds that of many organic and inorganic materials.

Abstract

Two-dimensional polymers (2DPs) and their layer-stacked covalent organic frameworks (2D COFs) offer modular, atomically precise platforms for organic optoelectronics, yet their photoconductive responses remain fundamentally constrained by strong excitonic effects and localized charge transport. Here, we demonstrate that a diyne-linked 2DP crystal with axial pyridine coordination overcomes this limitation, enabling simultaneous efficient free-carrier generation and band-like transport. Introducing pyridine ligands that axially coordinate to Cu-porphyrin nodes transforms weak van der Waals stacking into a pyridine-bridged architecture with pronounced interlayer band dispersion and substantially reduced carrier effective masses. The resulting strong interlayer electronic coupling suppresses the exciton binding energy to well below thermal energy, such that optical excitation directly populates delocalized electronic states. Time-resolved terahertz spectroscopy reveals Drude-type photoconductivity with room-temperature mobilities approaching 500 cm^2 V^-1 s^-1 and a photon-to-free-carrier conversion ratio of ~0.4, yielding a photoconductive response that exceeds that of state-of-the-art organic and many inorganic photoactive materials. These results establish interlayer coordination as a powerful strategy for mitigating excitonic effects and accessing inorganic-like charge transport in organic 2D crystals, opening a pathway toward highly efficient photo-to-electricity conversion in organic-based systems.