Ultrafast dynamics modulated by the number of central metal protons in 3d-orbitals metal complexes

IF 3.3 3区物理与天体物理 Q2 OPTICS

Journal of Luminescence Pub Date : 2024-12-10 DOI:10.1016/j.jlumin.2024.121005

Haixia Zhu , Zhaozhe Chen , Jun Li, Zhihui Chen , Si Xiao

{"title":"Ultrafast dynamics modulated by the number of central metal protons in 3d-orbitals metal complexes","authors":"Haixia Zhu , Zhaozhe Chen , Jun Li, Zhihui Chen , Si Xiao","doi":"10.1016/j.jlumin.2024.121005","DOIUrl":null,"url":null,"abstract":"<div><div>The lability of metal center, Jahn-Telller distortions, and structure-dependent energetics could influence the excited state dynamics of transition metal complexes to affect their application in photochemistry field. In this work, Co, Ni, and Cu-complexes, whose belong to 3d-orbitals metal complexes, are investigated by the time-resolved transient absorption (TA) spectrum upon 325 nm laser excitation. Their excited state dynamic shows the photobleaching in ultraviolet band and photoinduced absorption response in visible band. Compared to the ligand, the relaxation time at 350 nm remains in the range of 5.5 ps–9.4 ps, while a new fast relaxation appears as 160–290 fs at 450 nm. It is attributed to the intersystem crossing (ISC) from the <sup>1</sup>MLCT state to the <sup>3</sup>MLCT state transitions, which is side proofed by the decreasing lifetimes as the increasing numbers of shell electrons in central metal. This mechanism could be results in saturable absorption in ultraviolet band and reverse saturable absorption in visible band, which was confirmed by the Z-scan experiments. These finding provide insight into the photophysical mechanisms in 3d-metal-based complexes.</div></div>","PeriodicalId":16159,"journal":{"name":"Journal of Luminescence","volume":"278 ","pages":"Article 121005"},"PeriodicalIF":3.3000,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Luminescence","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022231324005696","RegionNum":3,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"OPTICS","Score":null,"Total":0}

引用次数: 0

Abstract

The lability of metal center, Jahn-Telller distortions, and structure-dependent energetics could influence the excited state dynamics of transition metal complexes to affect their application in photochemistry field. In this work, Co, Ni, and Cu-complexes, whose belong to 3d-orbitals metal complexes, are investigated by the time-resolved transient absorption (TA) spectrum upon 325 nm laser excitation. Their excited state dynamic shows the photobleaching in ultraviolet band and photoinduced absorption response in visible band. Compared to the ligand, the relaxation time at 350 nm remains in the range of 5.5 ps–9.4 ps, while a new fast relaxation appears as 160–290 fs at 450 nm. It is attributed to the intersystem crossing (ISC) from the ¹MLCT state to the ³MLCT state transitions, which is side proofed by the decreasing lifetimes as the increasing numbers of shell electrons in central metal. This mechanism could be results in saturable absorption in ultraviolet band and reverse saturable absorption in visible band, which was confirmed by the Z-scan experiments. These finding provide insight into the photophysical mechanisms in 3d-metal-based complexes.

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

Journal of Luminescence 物理-光学

CiteScore

6.70

自引率

13.90%

发文量

850

审稿时长

3.8 months

期刊介绍： The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid. We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.