Structural and Photophysical Modulation of Au(I)-Pb(II) Chains by Solvent Inclusion: A Study of Solvatopolymorphs

Area of Science:

• Inorganic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Gold(I) and lead(II) complexes are explored for unique electronic and structural properties.
• Heterometallic polymers offer tunable characteristics for advanced material applications.
• Solvatochromism, the color change with solvent, is a key phenomenon in responsive materials.

Purpose of the Study:

• To synthesize and characterize a new gold-(I)-lead-(II) heterometallic polymeric complex.
• To investigate the complex's solvatochromic and luminescent behavior in different solvent environments.
• To elucidate the electronic origins of the observed photophysical properties using computational methods.

Main Methods:

• Synthesis of the gold-lead heterometallic polymer and its solvatopolymorphs.
• Structural characterization using X-ray diffraction.
• Photophysical studies including absorption and emission spectroscopy.
• Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) calculations.

Main Results:

• A new gold-(I)-lead-(II) heterometallic polymer, [{Au-(C6F5)2}2{Pb-(S-Terpy)}]n, and its solvatopolymorphs were successfully synthesized.
• The complex displayed reversible solvatochromism, with significant changes in color and luminescence intensity modulated by solvent inclusion (e.g., acetone, diethyl ether).
• X-ray diffraction confirmed the persistence of trinuclear Au-Pb-Au units, while DFT/TD-DFT attributed emission to metal-to-ligand or ligand-to-ligand charge transfer transitions.

Conclusions:

• The synthesized gold-lead supramolecular systems exhibit tunable luminescent properties dependent on solvent interactions.
• The reversible solvatochromic behavior highlights their potential as responsive luminescent materials.
• These findings open avenues for developing novel sensors based on gold-lead heterometallic complexes.