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Area of Science:

  • Organometallic Chemistry
  • Materials Science
  • Photochemistry

Background:

  • Iridium complexes are known for their photoluminescent properties.
  • Developing responsive materials for sensing applications is an active area of research.
  • Aggregation-induced emission (AIE) and phosphorescence are key phenomena in luminescent materials.

Purpose of the Study:

  • To synthesize and characterize a new iridium(iii) complex with aggregation-induced phosphorescence (AIP) properties.
  • To investigate the complex's response to varying pH and its potential as a phosphorescent acid sensor.
  • To explore the complex's utility as a chemosensor for organic vapors and as a solvatochromic probe.

Main Methods:

  • Synthesis of the iridium(iii) complex [Ir(PPh3)2(bipy-H)(Cl)(H)] from 2,2'-bipyridine and iridium(iii).
  • Spectroscopic analysis (emission, absorption, 1H NMR) under varying acidic and basic conditions.
  • Density Functional Theory (DFT) calculations to understand the electronic properties and sensing mechanism.

Main Results:

  • The synthesized complex, [Ir(bipy-H)], displays "rollover" behavior and aggregation-induced phosphorescence (AIP).
  • Reversible emission color changes (bluish-green to yellowish-orange) were observed upon protonation and deprotonation, indicating sensitivity to acids.
  • The complex functions as a phosphorescent acid sensor in solution and solid states, and as a chemosensor for acidic/basic organic vapors.
  • The protonated form acts as a solvatochromic probe for oxygen-containing solvents and exhibits vapochromism.

Conclusions:

  • The iridium complex [Ir(bipy-H)] demonstrates reversible protonation/deprotonation-induced emission tuning, making it a versatile phosphorescent sensor.
  • Its sensitivity to acids and ability to detect organic vapors highlight its potential in chemical sensing.
  • DFT calculations confirm that changes in electron affinity of pyridinyl rings drive the observed responsive behaviors.