Fluorination Modulates Solid-State Reactivity and Guest Confinement in Organoboronic Ester Adducts

Area of Science:

• Materials Science
• Organic Chemistry
• Supramolecular Chemistry

Background:

• Organoboronic acids are versatile building blocks in supramolecular chemistry.
• Fluorination is a key strategy for tuning molecular properties.
• Self-assembly of molecular components is crucial for creating functional materials.

Purpose of the Study:

• To investigate the effect of fluorination on the self-assembly and properties of organoboronic acid adducts.
• To explore the formation of photoactive solids and guest encapsulation.
• To understand the structure-property relationships driven by fluorination patterns.

Main Methods:

• Synthesis of organoboronic acid adducts with varying fluorination levels.
• Crystallographic analysis to determine solid-state structures.
• Molecular modeling and Hirshfeld surface analysis to probe intermolecular interactions.

Main Results:

• T-shaped B←N adducts were formed through self-assembly.
• Adducts with up to two fluorine atoms exhibited photoactivity via [2+2]-photodimerization, driven by π…π stacking and C-H…π interactions.
• Adducts with higher fluorination levels formed photostable architectures encapsulating benzene, stabilized by C-H…F, C-H…O, and C-H…π contacts.

Conclusions:

• Fluorination of organoboronic systems is an effective strategy for engineering molecular material properties.
• The level and pattern of fluorination dictate whether adducts form photoactive dimers or photostable guest-encapsulating architectures.
• Understanding intermolecular interactions is key to designing materials with specific functionalities.