The First Coordination Polymers Based on 1,3-Diphosphaferrocenes and 1,1',2,3',4-Pentaphosphaferrocenes

Area of Science:

• Supramolecular chemistry
• Organometallic chemistry
• Polymer chemistry

Background:

• Phosphaferrocenes are effective building blocks for supramolecular assemblies.
• Coinage metal salts facilitate the formation of oligomeric and polymeric structures.

Purpose of the Study:

• To synthesize novel phosphaferrocenes with specific ligand structures.
• To investigate the self-assembly of these phosphaferrocenes with copper halides.
• To explore the formation of 1D and 2D polymeric architectures.

Main Methods:

• Synthesis of novel phosphaferrocenes featuring 1,3-P2C3iPr3 and/or 1,2,4-P3C2iPr2 ligands.
• Self-assembly reactions of synthesized phosphaferrocenes with CuI halides.
• Characterization of the resulting polymeric structures using appropriate analytical techniques.

Main Results:

• Formation of 1D polymers (infinite chains) with [Cp*Fe(η5-P2C3iPr3)].
• Formation of 1D ladderlike structures with [(η5-P3C2iPr2)Fe(η5-P2C3iPr3)].
• Construction of 2D networks with intact sandwich complexes using [Cp*Fe(η5-P3C2iPr2)], an uncommon outcome.

Conclusions:

• The study presents the first polymers incorporating di- and pentaphosphaferrocenes.
• The choice of phosphaferrocene ligand dictates the dimensionality and topology of the resulting polymer.
• The findings expand the scope of phosphaferrocene-based materials in supramolecular chemistry.