Synthesis and Functionalization of Isomeric Sesquihomodiamantenes

Area of Science:

• Organic Chemistry
• Materials Science
• Computational Chemistry

Background:

• Diamondoids are cage-like hydrocarbons with potential applications in materials science.
• Functionalization of C-H bonds in diamondoids is crucial for developing new materials.
• Understanding the electronic properties of diamondoid derivatives is key to their application.

Purpose of the Study:

• To prepare and structurally characterize anti- and syn-sesquihomodiamantanes (SDs).
• To investigate the CH-bond functionalization of SDs and parent sesquihomoadamantene.
• To correlate computational ionization potentials with experimental oxidation potentials and assess the stability of reduced/ionized states.

Main Methods:

• Synthesis and structural characterization of anti- and syn-sesquihomodiamantanes.
• CH-bond functionalization using a phase-transfer protocol.
• Density Functional Theory (DFT) computations for ionization potentials.
• Cyclic voltammetry for experimental oxidation potentials.

Main Results:

• Successful preparation and characterization of anti- and syn-SDs.
• Effective CH-bond functionalization achieved via phase-transfer catalysis.
• Good correlation between DFT-computed ionization potentials and experimental oxidation potentials.
• Stable reduced and ionized states of SDs due to β-hydrogen sheltering.

Conclusions:

• Anti- and syn-sesquihomodiamantanes are stable diamondoid structures.
• These SDs exhibit persistent reduced and ionized states.
• SDs show promise as building blocks for diamond materials with high stability and carrier mobility.