A ReaxFF-based thermomechanical analysis of N-carbophenes: phase-change, thermal expansion, and high temperature synthesis pathway

TL;DR

This study uses ReaxFF-based molecular dynamics to analyze the thermal stability, phase transitions, and thermal expansion of N-carbophenes, revealing their stability above 1000 K and a new phase transformation pathway.

Contribution

It provides the first detailed thermomechanical analysis of N-carbophenes, including stability limits, phase-change mechanisms, and effects of functionalization, using reactive MD simulations.

Findings

N-carbophenes remain stable above 1000 K.

Phase-change temperature decreases with longer N-phenylene chains.

Functional groups modulate thermal expansion behavior.

Abstract

N-carbophenes are a class of two-dimensional covalent organic frameworks with potential for solid-state gas storage and as 2D topological materials. Previous studies have demonstrated that variations in their bonding, topology, and functionalization enable the tuning of their chemical, electrical, and mechanical properties. Yet, the thermal stability and high-temperature behavior of pristine and functionalized N-carbophenes remain unexplored. Using ReaxFF-based reactive molecular dynamics (RMD) simulations with extensive statistical validation, we performed temperature-ramp MD simulations of pristine and functionalized N-carbophenes. We demonstrate that N-carbophenes remain stable up to temperatures above 1000 K. The phase-change onset temperatures decrease as the N-phenylene chain length increases in pristine N-carbophenes, attributed to increasing antiaromaticity in the central phenylene segments, thereby contributing to the foundational understanding of aromatic versus antiaromatic bonding in 2D carbon networks, a topic of considerable interest in theoretical chemistry. Pristine N-carbophenes exhibit negative area thermal expansion (NATE), whereas functional groups modulate this, leading to either negative or positive expansion. Functional groups remain stably bonded well above the transition temperature. We also show that a temperature-induced phase transition from graphenylene (2-carbophene) to {\gamma}-graphyne is possible. Our results provide upper bounds on N-carbophene stability, clarify the relationships between structure and thermal properties, and identify a new transformation pathway. These results will have applications in tunable band gaps, porous architectures, or chemically accessible sites.