# Carboxylate positional isomerism in metallacycles governs hierarchical assembly pathways

## TL;DR

Positional isomerism in metal-organic cycles influences how materials assemble, affecting their structure and properties at different scales.

## Contribution

The study reveals how isomeric variations in metal–organic cycles trigger structural effects that influence hierarchical assembly pathways.

## Key findings

- Isomeric variations in metal–organic cycles reconfigure noncovalent interaction networks.
- Positional isomerism diverts assembly pathways to produce distinct mesoscale architectures.
- The work provides insights into information transfer across different length scales in material assembly.

## Abstract

Positional isomerism plays a pivotal role in governing the assembly pathways of hierarchical architectures by modulating both the thermodynamic landscape and kinetic trajectories through precise spatial control of the constituent units, ultimately dictating the assembly efficacy and structural outcomes. Elucidating the underlying selectivity mechanisms of such isomerism offers fundamental insights into the rational design of advanced functional materials with tailored properties. Our findings reveal that isomeric variations in metal–organic cycles (MOCs) at the molecular scale trigger a cascade of structural effects—reconfiguring noncovalent interaction networks (particularly hydrogen bonding), diverting hierarchical assembly pathways, and ultimately generating distinct mesoscale architectures (extralong fibers and wide ribbons) with divergent physicochemical properties—thereby providing fundamental mechanistic insights into information transfer across length scales.

Positional isomerism plays a pivotal role in governing the assembly pathways of hierarchical architectures through precise spatial control of the constituent units, ultimately dictating the assembly efficacy and structural outcomes.