Mechanistic Investigation of the Synthesis of Dianionic In-Derived Coordination Polymers

Area of Science:

• Materials Science
• Inorganic Chemistry
• Computational Chemistry

Background:

• The formation mechanisms of crystalline coordination polymers are intricate and not fully understood.
• Investigating these mechanisms is crucial for designing novel materials with tailored properties.

Purpose of the Study:

• To elucidate the formation pathway of specific indium-based coordination polymers (YCM-22 and YCM-51).
• To establish a general methodology for studying the formation of crystalline coordination polymers.

Main Methods:

• Utilized a combination of density functional theory (DFT) analysis, synthetic chemistry, and in situ Raman spectroscopy.
• Investigated the role of potential intermediate species, such as [InCl4]- and [In(CO2R)Cl3]-.
• Isolated and characterized a molecular dimeric indium species (8a) as a precursor.

Main Results:

• DFT predicted two possible formation pathways for the coordination polymers.
• Identified [InCl4]- as an initial intermediate that forms at the expense of the target [In(CO2R)2X3]2- molecular building unit (MBU).
• In situ Raman spectroscopy confirmed the transient formation of [InCl4]- during YCM-22 synthesis.

Conclusions:

• Proposed a detailed mechanism for the formation of one-dimensional indium-derived coordination polymers.
• The findings provide a foundational roadmap for investigating the formation of other crystalline coordination polymers.