3BrY nucleation: from dimers to needle-like clusters

TL;DR

This study uses molecular modeling to explore the nucleation and growth of 3BrY clusters, revealing the formation of amorphous intermediates that evolve into elongated, needle-like structures similar to experimental observations.

Contribution

It provides a detailed molecular-level understanding of 3BrY nucleation and growth, highlighting the formation of transient amorphous clusters and their evolution into needle-like crystals.

Findings

Disordered clusters of 10-15 monomers spontaneously form from solution.

Larger clusters develop elongated, needle-like morphologies.

Growth involves continuous rearrangement and exchange of molecules with solution.

Abstract

The nucleation of 1,3,5-Tris(4-bromophenyl)- benzene (3BrY) occurs through the formation of amorphous intermediates. However, a detailed experimental characterization of the structural and dynamic features of such early- stage precursors is prevented by their transient nature. In this work, we apply molecular mod- eling to investigate both nucleation and growth of 3BrY clusters from solution. Consistently with experimental findings, we observe that dis- ordered clusters consisting of 10-15 monomers can spontaneously emerge from solution. Such clusters are poorly ordered and can easily fluctuate in size and shape. When clusters grow to a larger size (up to 200 monomer units) they develop a markedly elongated morphology, reminiscent of the needle-like 3BrY crystals observed experimentally. The growth process is characterized by a continuous rearrangement of ordered and disordered domains accompa- nied by a dynamical exchange of molecules and oligomers with the solution, in a mechanism resembling the self-assembly of non-covalent supra-molecular fibers.