Theoretical study on counter anion- and solvent-dependent fluorescence quenching mechanism of 2-phenylbenzo[b]phospholium salts

Atomically precise metal nanoclusters (MNCs), as a potential type of photoacoustic (PA) contrast agent, are limited in application due to their low PA conversion efficiency (PACE). Here, with hydrophilic Au25SR18 (SR = thiolate) as model NCs, we present a result that weakly polar solvent induces aggregation, which effectively enhances PA intensity and PACE. The PA intensity and PACE are highly dependent on the degree of aggregation, while the aggregation‐enhanced PA intensity (AEPA) positively correlates to the protected ligands. Such an AEPA phenomenon indicates that aggregation actually accelerates the intramolecular motion of Au NCs, and enlarges the proportion of excited state energy dissipated through vibrational relaxation. This result conflicts with the restriction of intramolecular motion mechanism of aggregation‐induced emission. Further experiments show that the increased energy of AEPA originates from the aggregation inhibiting the intermolecular energy transfer from excited Au NCs to their surrounding medium molecules, including solvent molecule and dissolved oxygen, rather than restricting radiative relaxations. This study develops a new strategy for enhancing the PA intensity of Au NCs, and contributes to a deeper understanding of the origin of the PA signal and the excited state energy dissipation processes for MNCs.

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Ligand‐dependent aggregation‐enhanced photoacoustic of atomically precise metal nanocluster

Zhou

Wang

Yao

et al. 2023

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Photochemical Synthesis of Polycyclic Phosphonium Salts as Efficient Anticancer and Antibacterial Agents

Li,

Zhuang,

Dong

et al. 2024

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Phosphorus‐containing functional materials have diverse applications in optoelectronics and bioscience owing to their unique properties. However, polycyclic π‐conjugated phosphonium salts have been rarely explored due to their complex synthesis. In this work, a facile and efficient method for constructing polycyclic π‐conjugated phosphonium salts (TBPIMe derivatives) is proposed, based on the photocyclization of phosphindolium salts (TPPIMe derivatives). Systematic experimental and theoretical investigations reveal the changed photophysical and photochemical properties when TPPIMe derivatives are converted to TBPIMe derivatives. Notably, the novel polycyclic π‐conjugated phosphonium salt p‐MOTBPIMe exhibits improved reactive oxygen species generation ability and much stronger specific affinity toward DNA than phosphindolium salts p‐MOTPPIMe. Moreover, in vitro experiments demonstrate that p‐MOTPPIMe can also be efficiently converted into p‐MOTBPIMe under 405 nm laser irradiation in living cells, accompanied by the migration from cytoplasm to nucleus to enhance the photodynamic effect. Additionally, p‐MOTBPIMe shows superior antibacterial activity against not only Gram‐positive drug‐resistant bacteria but also fungi, by leveraging both dark and light cytotoxicity. This work opens up a new chemical toolkit for novel polycyclic π‐conjugated phosphonium salts, which are promising for developing advanced theranostic agents with satisfactory accuracy and efficacy.

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A Study of 2,3,4,5-tetrakis(2-thienyl)-1-monophosphole and 2,3,4,5-tetrakis(2-thienyl)-1-monophosphaferrocene as building blocks for π-conjugated systems

Zagidullin,

Lakomkina,

Gerasimova

et al. 2024

Journal of Organometallic Chemistry

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Theoretical study on counter anion- and solvent-dependent fluorescence quenching mechanism of 2-phenylbenzo[b]phospholium salts

Cited by 5 publications

References 30 publications

Ligand‐dependent aggregation‐enhanced photoacoustic of atomically precise metal nanocluster

Ligand‐dependent aggregation‐enhanced photoacoustic of atomically precise metal nanocluster

Photochemical Synthesis of Polycyclic Phosphonium Salts as Efficient Anticancer and Antibacterial Agents

A Study of 2,3,4,5-tetrakis(2-thienyl)-1-monophosphole and 2,3,4,5-tetrakis(2-thienyl)-1-monophosphaferrocene as building blocks for π-conjugated systems

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