Highly fluorescent 3-perylenyldiphenylphosphane compounds: An experimental and theoretical study

IF 4.1 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-02-04 DOI:10.1016/j.dyepig.2025.112690

J. Emilio Expósito , Sergio Lentijo , Gabriel Aullón , Manuel Bardají , Jesús A. Miguel

{"title":"Highly fluorescent 3-perylenyldiphenylphosphane compounds: An experimental and theoretical study","authors":"J. Emilio Expósito , Sergio Lentijo , Gabriel Aullón , Manuel Bardají , Jesús A. Miguel","doi":"10.1016/j.dyepig.2025.112690","DOIUrl":null,"url":null,"abstract":"<div><div>The perylene derivative, 3-perylenyldiphenylphosphane (PPh2Per, 1), was prepared and used to synthesize the oxidized P(V) compounds A = PPh2Per (A = O (2); A = S (3)). Substitution reactions led to mononuclear gold(I) complexes [AuX(PPh2Per)] (X = Cl (4); X = C6F5 (5)), [AuX(S=PPh2Per)] (X = Cl (6); X = C6F5 (7)) and palladium(II) complexes trans-[Pd(C6F5)2(PPh2Per)2] (8). X-ray single crystal studies of compounds 5 and 7 confirmed the expected structures. The UV–Vis absorption spectra display intense peaks in the visible region with maxima from 454 to 461 nm. A DFT study was performed for the absorption spectra of ligands and complexes, showing that the lowest most intense transition is a HOMO → LUMO transition in the perylene core, although affected by functional group and metallic fragment. The ligands and their complexes are fluorescent in solution, due to the perylene fragment, showing an emission in the range 450–550 nm, with maxima from 467 to 472 nm. Quantum yield starts at 13 % for the phosphane and increases dramatically to the range of 63–87 % after oxidation or coordination to a metal fragment. This work illustrates how the PET effect can be used to recover the initial extremely intense emission of free unfunctionalized perylene ring system.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112690"},"PeriodicalIF":4.1000,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dyes and Pigments","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0143720825000609","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}

引用次数: 0

Abstract

The perylene derivative, 3-perylenyldiphenylphosphane (PPh₂Per, 1), was prepared and used to synthesize the oxidized P(V) compounds A = PPh₂Per (A = O (2); A = S (3)). Substitution reactions led to mononuclear gold(I) complexes [AuX(PPh₂Per)] (X = Cl (4); X = C₆F₅ (5)), [AuX(S=PPh₂Per)] (X = Cl (6); X = C₆F₅ (7)) and palladium(II) complexes trans-[Pd(C₆F₅)₂(PPh₂Per)₂] (8). X-ray single crystal studies of compounds 5 and 7 confirmed the expected structures. The UV–Vis absorption spectra display intense peaks in the visible region with maxima from 454 to 461 nm. A DFT study was performed for the absorption spectra of ligands and complexes, showing that the lowest most intense transition is a HOMO → LUMO transition in the perylene core, although affected by functional group and metallic fragment. The ligands and their complexes are fluorescent in solution, due to the perylene fragment, showing an emission in the range 450–550 nm, with maxima from 467 to 472 nm. Quantum yield starts at 13 % for the phosphane and increases dramatically to the range of 63–87 % after oxidation or coordination to a metal fragment. This work illustrates how the PET effect can be used to recover the initial extremely intense emission of free unfunctionalized perylene ring system.

Abstract Image

查看原文本刊更多论文

求助全文

约1分钟内获得全文求助全文

来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.