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Featuring long-lifetime deep-red emitting iridiumIII complexes with high colour purity: insights into the excited state dynamics from spectroscopic and theoretical perspectives.
Silva, Renan C; Canisares, Felipe S M; Saraiva, Leonardo F; Pires, Ana M; Lima, Sergio A M.
Afiliação
  • Silva RC; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, SP, Brazil. renan.caike@unesp.br.
  • Canisares FSM; São Paulo State University (Unesp), Institute of Biosciences, Humanities and Exact Sciences, São José do Rio Preto, SP, Brazil.
  • Saraiva LF; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, SP, Brazil. renan.caike@unesp.br.
  • Pires AM; São Paulo State University (Unesp), Institute of Chemistry, Araraquara, SP, Brazil.
  • Lima SAM; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, SP, Brazil. renan.caike@unesp.br.
Dalton Trans ; 53(12): 5466-5477, 2024 Mar 19.
Article em En | MEDLINE | ID: mdl-38414337
ABSTRACT
The significant attention drawn to IrIII-complexes in recent years has boosted the development of new compounds with advantageous photophysical features. However, obtaining IrIII deep-red-emitting complexes with long lived excited state, high colour purity and high quantum yield (Φ) remains a challenging task. To address this issue, this study reports the synthesis and photophysical investigation of three novel zwitterionic complexes, [Ir(C^N)2bqdc] (C^N = ppy, phq, and bzq), with ppy = 2-phenylpyridine (Ir-pb), phq = 2-phenylquinoline (Ir-qb), bzq = benzo[h]quinoline (Ir-bb), and bqdc = potassium 2,2'-biquinoline-4,4'-dicarboxylate. These complexes exhibit high quantum yields and long emission lifetimes with high colour purity in the deep-red region. The structural characterisation carried out by usual spectroscopic measurements supports the proposed structures, while the photophysical study unveiled the high contribution of the 3MLCT state to the hybrid emitter state, as endorsed by theoretical investigations. The desired correspondence between the calculations and the experimental data set affirmed the accuracy of the theoretical analysis, which enabled us to establish a relationship between the ground-to-excited-state geometry distortion and the lifetime through the nonradiative decay (knr). Furthermore, these newly synthesized complexes exhibit quenching in the presence of molecular oxygen. In deoxygenated DMSO solution the knr values halve, increasing the quantum yields (34.0, 10.6, and 26.6%) and the lifetimes (1.13, 1.11, and 1.72 µs), while leading to quite pure deep-red emission - CIE coordinates (0.67, 0.33), (0.60, 0.40;), (0.65, 0.35) for Ir-pb, Ir-qb, and Ir-bb, respectively. These complexes display considerable potential for a wide range of applications, such as photodynamic therapy, due to their attractive photophysical properties, and are among the deep-red-emitting complexes reported in the literature with longer lifetimes and higher Φ.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Dalton Trans Assunto da revista: QUIMICA Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Brasil País de publicação: Reino Unido

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Dalton Trans Assunto da revista: QUIMICA Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Brasil País de publicação: Reino Unido