Structure-Property Relationships of Inorganic-Organic Hybrid Semiconducting Se-Fe-Cu-CO Polymers

Area of Science:

• Materials Science
• Inorganic Chemistry
• Supramolecular Chemistry

Background:

• Synthesis of novel inorganic-organic-hybrid polymers is crucial for developing advanced functional materials.
• Understanding structure-property relationships in metal-organic frameworks and coordination polymers is an active research area.
• Liquid-assisted grinding (LAG) offers a green and efficient method for synthesizing complex materials.

Purpose of the Study:

• To synthesize a novel family of inorganic-organic-hybrid copper polymers incorporating [SeFe3(CO)9]2- clusters and dipyridyl ligands.
• To investigate the dimensionality transformations and tunable electronic properties of these polymers.
• To evaluate their potential applications in photodegradation of pollutants.

Main Methods:

• Three-component liquid-assisted grinding (LAG) synthesis using [Cu(MeCN)4]+, [SeFe3(CO)9]2- cluster (1), and various dipyridyl ligands (dpy, bpee, bpea, bpp).
• Characterization of polymer structures, including dimensionality and coordination modes.
• Measurement of optical and electrical properties (energy gaps, electrical conductivity), supported by XPS, XANES, and DFT calculations.
• Assessment of photodegradation efficiency towards nitroaromatics and organic dyes.

Main Results:

• Successfully synthesized four types of inorganic-organic-hybrid Cu polymers: cluster-linked 2D, cluster-pendant 1D, and cluster-blocked 1D.
• Achieved reversible dimensionality transformations by adjusting LAG conditions.
• Demonstrated tunable low-energy gaps (1.49-1.72 eV) and semiconducting behavior, with conductivity correlating to energy gaps.
• Identified C-H···O hydrogen bonds and C-H···π contacts as key factors for semiconductivity in conjugation-interrupted polymers.
• Exhibited excellent water/light stability and efficient pseudo-first-order photodegradation of pollutants, with cluster-linked 1-bpp-2D showing superior performance.

Conclusions:

• The synthesized inorganic-organic-hybrid Cu polymers exhibit tunable electronic properties and semiconducting behavior.
• The structural features, particularly the role of the [SeFe3(CO)9]2- cluster, significantly influence the electronic properties.
• These stable and efficient polymers show great potential for environmental remediation applications, such as pollutant degradation.