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Creators/Authors contains: "Brown, Ryan D."

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  1. Abstract The polymerization of 1,4‐benzenediboronic acid (BDBA) on mica to form a covalent organic framework (COF‐1) reveals a dramatic increase in crystallinity when physically confined by exfoliated graphene. COF‐1 domains formed under graphene confinement are highly geometric in shape and on the order of square micrometers in size, while outside of the exfoliated flakes, the COF‐1 does not exhibit long‐range mesoscale structural order, according to atomic force microscopy imaging. Micro‐Fourier transform infrared spectroscopy confirms the presence of COF‐1 both outside and underneath the exfoliated graphene flakes, and density functional theory calculations predict that higher mobility and self‐assembly are not causes of this higher degree of crystallinity for the confined COF‐1 domains. The most likely origin of the confined COF‐1's substantial increase in crystallinity is from enhanced dynamic covalent crystallization due to the water confined beneath the graphene flake. 
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