Exploring the Co-Crystallization Landscape of One-Dimensional Coordination Polymers Using a Molecular Electrostatic...

Area of Science:

• Materials Science
• Crystallography
• Supramolecular Chemistry

Background:

• Coordination polymers (CPs) offer potential for multicomponent materials.
• Retaining parent CP structural integrity during heteromeric material formation is challenging.

Purpose of the Study:

• To investigate the use of molecular electrostatic potential (MEP) driven co-crystallization for creating multicomponent coordination polymers.
• To identify effective co-former design principles for successful integration into CP architectures.

Main Methods:

• Utilized MEP calculations to evaluate the activation of hydrogen-bond donors in thirteen co-formers.
• Performed co-crystallization experiments between nine CP families and seven selected co-formers.
• Structurally characterized successful co-crystalline compounds using X-ray diffraction.

Main Results:

• Six successful co-crystallizations were achieved out of twenty-one attempts.
• Four compounds were structurally characterized, confirming the formation of intended hydrogen bonds.
• MEP analysis correlated with co-former effectiveness, identifying key structural and electrostatic requirements.

Conclusions:

• Molecular electrostatic potential-driven co-crystallization is a viable strategy for designing multicomponent coordination polymers.
• Effective co-formers require highly activated hydrogen-bond donors and specific orientations of electron-withdrawing groups.
• This approach enables the rational design of complex 3D architectures from 1D CP building units.