Self-Assembly of Diboronic Esters with U-Shaped Bipyridines: "Plug-in-Socket" Assemblies

Area of Science:

• Supramolecular Chemistry
• Organoboron Chemistry
• Materials Science

Background:

• Self-assembly is a key strategy for constructing complex molecular architectures.
• Diboronic acids and pyridyl-based ligands are versatile building blocks in supramolecular chemistry.
• Understanding donor-acceptor interactions is crucial for designing functional materials.

Purpose of the Study:

• To synthesize and characterize novel self-assembled complexes using 1,3-diboronic acid and U-shaped pyridyl donors.
• To investigate the structural and electronic properties of the resulting two-component assemblies.
• To explore the potential of these materials in the design of boron-based supramolecular structures.

Main Methods:

• Utilized ditopic dative bond acceptor 1,3-diboronic acid.
• Employed U-shaped pyridyl donors: 1,8-bis(4-pyridyl)naphthalene (DPN), 1,8-bis(4-ethylenylpyridyl)naphthalene (DEPN), and 1,8-bis(4-ethynylpyridyl)naphthalene (DAPN).
• Characterized assemblies using DFT calculations and analyzed packing via π-π interactions.

Main Results:

• Discrete two-component structures with "plug-in-socket" geometries were successfully formed.
• DFT calculations confirmed electron-poor pyridyl donors and electron-rich catecholate acceptors.
• Assemblies exhibited π-π stacking and demonstrated solvent inclusion capabilities (DPN, DAPN).

Conclusions:

• The synthesized complexes represent a novel class of self-assembled boron-based structures.
• The observed "plug-in-socket" geometry and electronic properties are promising for molecular recognition and design.
• These findings provide a foundation for developing advanced supramolecular dyads and other complex boron-containing materials.