Coordination Polymer-Mediated Molecular Surgery for Precise Interconversion of Dicyclobutane Compounds

Area of Science:

• Coordination Chemistry
• Materials Science
• Organic Synthesis

Background:

• Coordination polymers offer tunable structures for advanced applications.
• Precise control over organic transformations within solid-state materials remains a challenge.

Purpose of the Study:

• To develop a cadmium-based coordination polymer for stereoselective synthesis of cyclobutane isomers.
• To investigate the interconversion of these isomers via molecular surgery within the polymer framework.

Main Methods:

• Synthesis of a Cd(II)-based coordination polymer using Cd(II) salt, 5-fluoro-1,3-bis[2-(4-pyridyl)ethenyl]benzene (5-F-1,3-bpeb), and p-fluorobenzoic acid (HFBA).
• Photochemical and thermal treatment to induce cyclobutane formation and isomerization.
• Characterization using nuclear magnetic resonance (NMR), in situ powder X-ray diffraction (PXRD), and IR spectroscopy.

Main Results:

• Formation of a 1D coordination polymer chain with face-to-face arrangement of 5-F-1,3-bpeb ligands.
• Stereoselective production of various cyclobutane isomers (mono- and di-cyclobutanes) upon UV irradiation and heating.
• Demonstration of isomer interconversion through bond cutting/coupling, akin to molecular surgery, controlled by thermal stability and reactant alignment.

Conclusions:

• The developed coordination polymer acts as a platform for controlled skeletal editing.
• This method allows for the construction of complex organic compounds from a single precursor via isomer interconversion.
• The findings present a novel strategy for solid-state organic synthesis and molecular manipulation.