Theoretical Calculations for Highly Selective Direct Heteroarylation Polymerization: New Nitrile-Substituted...

Area of Science:

• Materials Science
• Polymer Chemistry
• Organic Electronics

Background:

• Direct Heteroarylation Polymerization (DHAP) offers an alternative to traditional synthesis of π-conjugated polymers.
• Theoretical calculations of C-H bond activation energy (Ea) have previously aided in predicting DHAP selectivity.
• Organic electronics rely on π-conjugated polymers synthesized via methods like DHAP.

Purpose of the Study:

• To compile and expand theoretical calculations of Ea for C-H bonds in common organic electronic moieties.
• To investigate the impact of substituents on the Ea of dithienyl-diketopyrrolopyrrole (DT-DPP) derivatives.
• To synthesize and characterize new cyanated DT-DPP (CNDT-DPP) monomers and polymers using DHAP.

Main Methods:

• Gathering and performing theoretical calculations of C-H bond activation energies (Ea).
• Utilizing Density Functional Theory (DFT) for computational analysis.
• Synthesizing new CNDT-DPP monomers and polymers via Direct Heteroarylation Polymerization (DHAP).
• Characterizing the electro-optical properties of synthesized materials.

Main Results:

• Theoretical calculations demonstrate significant modulation of C-H bond Ea in DT-DPP derivatives with bromine or electron-withdrawing groups (fluorine, nitrile).
• New CNDT-DPP monomers and copolymers were successfully synthesized using DHAP.
• The electro-optical properties of the new cyanated polymers were evaluated and compared to analogues.

Conclusions:

• Theoretical Ea calculations are effective for rationalizing and predicting DHAP selectivity.
• Substitution on the thienyl moiety of DT-DPP strongly influences C-H bond reactivity.
• The study provides new insights into the synthesis and properties of CNDT-DPP based π-conjugated polymers for organic electronics.