Pressure-Engineered Through-Space Conjugation for Precise Control of Clusteroluminescence

Area of Science:

• Materials Science
• Photophysics
• Supramolecular Chemistry

Background:

• Clusteroluminogens (CLgens) are nonconjugated luminophores utilizing through-space conjugation (TSC).
• Controlling TSC in CLgens for tailored optical properties is challenging.
• Conventional π-conjugated luminophores have inherent limitations.

Purpose of the Study:

• To develop a novel strategy for engineering TSC in tetraphenylalkanes (TPAs)-based CLgens using high pressure.
• To elucidate the structure-property relationships governing CLgen luminescence under pressure.
• To customize optical properties and emission characteristics of CLgens.

Main Methods:

• Application of high pressure to TPAs-based CLgens.
• Molecular-level structural analysis under compression and decompression.
• Spectroscopic characterization of luminescence changes.

Main Results:

• Initial compression caused molecular distortions, diminishing TSC and leading to hypochromatic shifts.
• Further compression enhanced TSC and suppressed motion, resulting in intensified and bathochromic-shifted emission.
• Pressure release induced irreversible structural changes, yielding intense white-light emission.

Conclusions:

• High pressure is an effective tool for manipulating TSC and optical properties of CLgens.
• Understanding structural factors is crucial for controlling TSC.
• This work provides insights for developing new photophysical theories in aggregate science.