Ferrocenyl naphthalenes: substituent- and substitution pattern-depending charge transfer studies

Area of Science:

• Organometallic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Ferrocene and naphthalene are important building blocks in organometallic and materials science.
• Functionalized naphthalenes offer diverse electronic and structural properties.
• Cross-coupling reactions provide versatile routes to complex organic molecules.

Purpose of the Study:

• To synthesize a series of ferrocenyl-functionalized naphthalenes.
• To investigate their molecular structures using X-ray diffraction.
• To explore their electrochemical and spectroelectrochemical behavior.

Main Methods:

• Suzuki-Miyaura and Negishi C,C cross-coupling reactions.
• Synthesis of ferrocenylboronic acid (FcB(OH)2) and ferrocenylzinc chloride (FcZnCl).
• Single-crystal X-ray diffraction analysis and (spectro)electrochemical measurements.

Main Results:

• Successful synthesis of various mono- and di-ferrocenylnaphthalenes.
• X-ray structures reveal inter- and intramolecular π-interactions, including T-shaped and parallel displaced arrangements.
• Electrochemical studies show reversible redox events, influenced by substituent effects and naphthalene substitution patterns.
• Mixed-valent species exhibit weak electronic coupling (Class II systems).

Conclusions:

• Ferrocenyl-functionalized naphthalenes can be efficiently synthesized via cross-coupling reactions.
• The molecular structures exhibit diverse π-stacking motifs.
• Electrochemical properties are tunable by substitution and substitution patterns, impacting electron transfer pathways.
• These compounds represent promising candidates for advanced materials with tunable electronic properties.