Diamondoid-Type Copper Coordination Polymers Containing Soft Cyclodiphosphazane Ligands

Area of Science:

• Coordination Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Cyclodiphosphazanes are versatile ligands in coordination chemistry.
• Copper halide complexes offer diverse structural possibilities.
• Alkyne functionalization introduces unique reactivity and coordination modes.

Purpose of the Study:

• To synthesize novel coordination polymers from alkyne-appended cyclodiphosphazanes and copper halides.
• To investigate the influence of cyclodiphosphazane stereoisomers (cis and trans) on polymer formation.
• To explore unprecedented copper-alkyne coordination motifs.

Main Methods:

• Reaction of cis- and trans-alkyne-appended cyclodiphosphazanes with copper(I) bromide and iodide.
• Crystallization and structural characterization of the resulting coordination polymers.
• Analysis of coordination modes, including copper-alkyne interactions.

Main Results:

• Synthesis of three novel coordination polymers: two 3D and one 1D structure.
• The cis-isomer reacted with CuBr to form a 3D polymer with diamondoid topology and unprecedented copper-alkyne coordination.
• The cis-isomer reacted with CuI to form a 1D polymeric complex.
• The trans-isomer reacted with CuI to form a 3D polymer, independent of stoichiometry.

Conclusions:

• Stereochemistry of cyclodiphosphazanes significantly impacts the resulting coordination polymer structure.
• Novel copper-alkyne coordination modes have been achieved.
• The synthetic strategy provides access to diverse coordination polymer architectures.