Stepwise on-surface dissymmetric reaction to construct binodal organometallic network

Area of Science:

• Surface Science
• Organometallic Chemistry
• Nanotechnology

Background:

• Dissymmetric reactions are crucial for selective molecular functionalization but are difficult to achieve.
• Ordered nanostructures are essential for advanced materials and devices.
• Controlled synthesis of complex molecular architectures on surfaces remains a significant challenge.

Purpose of the Study:

• To demonstrate a dissymmetric reaction on a Ag(111) surface.
• To achieve stepwise functionalization of 1,4-dibromo-2,5-diethynylbenzene (2Br-DEB).
• To construct ordered two-dimensional organometallic networks with distinct node types.

Main Methods:

• Utilizing a stepwise activation strategy on a Ag(111) surface.
• Employing scanning tunneling microscopy (STM) for surface imaging.
• Applying density functional theory (DFT) calculations for mechanistic insights.

Main Results:

• Successfully realized the dissymmetric reaction of 2Br-DEB via sequential H-passivation and metalation.
• Formed one-dimensional organometallic chains with alkynyl-silver-alkynyl nodes at 300 K.
• Transformed chains into binodal 2D networks with alkynyl-silver-alkynyl and alkynyl-silver-phenyl nodes at 320–450 K.

Conclusions:

• The study exemplifies the successful achievement of dissymmetric reactions on surfaces.
• A stepwise activation strategy enables controlled fabrication of complex nanostructures.
• This approach opens avenues for designing ordered organometallic materials with tailored properties.