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<p>The photophysical behavior of functionalized derivatives of poly(9-vinylcarbazole) (PVK) was investigated to elucidate the influence of aggregation across different physical states. The modified polymer PVK-DBF, containing a dibenzofuran substituent, was compared with pristine PVK and PVK-Br to assess how molecular structure and aggregation affect their optical properties. Comprehensive optical and electrochemical characterizations, including UV–Vis spectroscopy, photoluminescence (PL), time-resolved PL, and cyclic voltammetry, were performed in solution, thin film, and powder states. PVK-DBF exhibited strong blue emission with narrower spectral width (FWHM = 48.0&#xa0;nm) and photoluminescence quantum yield (PLQY) comparable to PVK (12.08% vs 12.73%), resulting in improved color purity while preserving the characteristic emission profile of the PVK backbone. Aggregation studies showed a slight increase in PLQY to approximately 14% at low water fractions, followed by pronounced emission quenching at higher aggregation levels, evidencing the strong sensitivity of PVK-DBF emission to molecular packing and solvent environment. Dilution of PVK-DBF in a PMMA matrix partially suppressed aggregation-caused quenching, increasing its PLQY from 0.44% to 2.13% in thin films. Electrochemical analysis showed that DBF incorporation slightly stabilizes the HOMO and LUMO energy levels while preserving PVK’s intrinsic blue emission. These findings highlight the critical role of molecular design and aggregation control in governing emissive behavior across different physical states. Although PVK-DBF exhibits limited PLQY in neat thin films, its enhanced color purity and favorable photophysical performance suggest potential relevance for further investigation in optoelectronic materials, underscoring the strong influence of structural packing on the photophysical behavior of semiconductor polymers.</p>

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Influence of dibenzofuran substitution on the photophysical properties and emissive behavior of PVK across different physical states

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月13日

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  • Cleyton Marcos Siqueira Moreira,
  • Daniela Corrêa Santos,
  • Larissa Morais Viana,
  • Michelle Gonçalves Mothé,
  • Maria de Fátima Vieira Marques

摘要

The photophysical behavior of functionalized derivatives of poly(9-vinylcarbazole) (PVK) was investigated to elucidate the influence of aggregation across different physical states. The modified polymer PVK-DBF, containing a dibenzofuran substituent, was compared with pristine PVK and PVK-Br to assess how molecular structure and aggregation affect their optical properties. Comprehensive optical and electrochemical characterizations, including UV–Vis spectroscopy, photoluminescence (PL), time-resolved PL, and cyclic voltammetry, were performed in solution, thin film, and powder states. PVK-DBF exhibited strong blue emission with narrower spectral width (FWHM = 48.0 nm) and photoluminescence quantum yield (PLQY) comparable to PVK (12.08% vs 12.73%), resulting in improved color purity while preserving the characteristic emission profile of the PVK backbone. Aggregation studies showed a slight increase in PLQY to approximately 14% at low water fractions, followed by pronounced emission quenching at higher aggregation levels, evidencing the strong sensitivity of PVK-DBF emission to molecular packing and solvent environment. Dilution of PVK-DBF in a PMMA matrix partially suppressed aggregation-caused quenching, increasing its PLQY from 0.44% to 2.13% in thin films. Electrochemical analysis showed that DBF incorporation slightly stabilizes the HOMO and LUMO energy levels while preserving PVK’s intrinsic blue emission. These findings highlight the critical role of molecular design and aggregation control in governing emissive behavior across different physical states. Although PVK-DBF exhibits limited PLQY in neat thin films, its enhanced color purity and favorable photophysical performance suggest potential relevance for further investigation in optoelectronic materials, underscoring the strong influence of structural packing on the photophysical behavior of semiconductor polymers.