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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
Published on: February 7, 2017
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Impact of Rigidity on Molecular Self-Assembly
Ella M King1,2, Matthew A Gebbie1,3, Nicholas A Melosh1,4
1Geballe Laboratory for Advanced Materials , Stanford University , Stanford , California 94305 , United States.
Langmuir : the ACS Journal of Surfaces and Colloids
|October 16, 2019
Summary
Rigid diamondoids assemble uniquely due to their low entropic penalties, enabling novel nanomaterial construction. Tuning molecular rigidity offers a strategy for designing functional materials.
Area of Science:
- Materials Science
- Physical Chemistry
- Nanotechnology
Background:
- Rigid, cage-like molecules like diamondoids exhibit unique self-assembly behaviors.
- These behaviors include templating 1-D nanomaterial assembly through pathways typically blocked for bulky molecules.
Purpose of the Study:
- Investigate the molecular forces governing diamondoid self-assembly.
- Explore how high structural rigidity influences novel assembly pathways.
Main Methods:
- Calculated the distance-dependent impact of entropy on assembly using molecular dynamics simulations.
- Isolated pairwise entropic and enthalpic contributions by simulating molecules in a thermal bath.
- Compared diamondoids to linear alkanes to discern the effect of rigidity.
Main Results:
- Diamondoids experience lower entropic penalties during assembly compared to linear alkanes.
- The cage-like structure of diamondoids incurs an enthalpic penalty at contact, counterbalanced by entropic effects.
- Linear alkanes show stronger van der Waals interactions at contact due to less bulky structures.
Conclusions:
- Low entropic penalties for diamondoids explain their effectiveness in templating nanomaterial assembly.
- Molecular rigidity is a tunable parameter for controlling the assembly of functional materials.
- Findings support the development of biomimetic surfaces and advanced nanoscale materials.
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