Synthesis and Design of Metalloporphyrin Oligomers with Temperature-Assisted Spectral-Luminescent Properties

IF 1.8 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Russian Journal of Inorganic Chemistry Pub Date : 2024-04-12 DOI:10.1134/s0036023624600138

A. E. Likhonina, G. M. Mamardashvili, N. Z. Mamardashvili

{"title":"Synthesis and Design of Metalloporphyrin Oligomers with Temperature-Assisted Spectral-Luminescent Properties","authors":"A. E. Likhonina, G. M. Mamardashvili, N. Z. Mamardashvili","doi":"10.1134/s0036023624600138","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A number of metal-linked porphyrin oligomers of different structures were synthesized and their luminescent sensitivity to temperature was studied. Density functional theory (DFT) was used to geometrically optimize the resulting compounds structure. Coordination Sn(IV)-dipyridylporphyrin tetramers formed through the interaction of pyridyl fragments of the macrocycle with Pd(II) and Pt(II) cations, as well as the octamer assembled by coordination of pyridyl groups with Pd(II) cations and bis-chelate binding of bidentate ligands in the axial positions of Sn(IV)-porphyrins with the Cu(II) cation, were shown to exhibit fluorescent thermal sensitivity in the temperature range of 328–383 K in the region of 600–650 nm. In this section, the dependence of the fluorescence quantum yield (fluorescence intensity) with a temperature increase is a monotonic pseudolinear trend. The flare-up ranges from 1.5 to 4.5 times, depending on the structure of porphyrin oligomers. At temperatures above 383 K, all studied porphyrin assemblies obtained on the basis of Pd(II) exhibit a decrease in fluorescence intensity. At the same time, their structure is preserved. The porphyrin tetramer obtained from Pt(II) undergoes a structural rearrangement, transforming into a presumably cyclometalated organoplatinum compound that exhibits effective luminescence at 493 nm. The results obtained could be used for the development of new temperature-assisted optoelectronic devices such as sensors, molecular reactors and catalysts.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"65 1","pages":""},"PeriodicalIF":1.8000,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1134/s0036023624600138","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

A number of metal-linked porphyrin oligomers of different structures were synthesized and their luminescent sensitivity to temperature was studied. Density functional theory (DFT) was used to geometrically optimize the resulting compounds structure. Coordination Sn(IV)-dipyridylporphyrin tetramers formed through the interaction of pyridyl fragments of the macrocycle with Pd(II) and Pt(II) cations, as well as the octamer assembled by coordination of pyridyl groups with Pd(II) cations and bis-chelate binding of bidentate ligands in the axial positions of Sn(IV)-porphyrins with the Cu(II) cation, were shown to exhibit fluorescent thermal sensitivity in the temperature range of 328–383 K in the region of 600–650 nm. In this section, the dependence of the fluorescence quantum yield (fluorescence intensity) with a temperature increase is a monotonic pseudolinear trend. The flare-up ranges from 1.5 to 4.5 times, depending on the structure of porphyrin oligomers. At temperatures above 383 K, all studied porphyrin assemblies obtained on the basis of Pd(II) exhibit a decrease in fluorescence intensity. At the same time, their structure is preserved. The porphyrin tetramer obtained from Pt(II) undergoes a structural rearrangement, transforming into a presumably cyclometalated organoplatinum compound that exhibits effective luminescence at 493 nm. The results obtained could be used for the development of new temperature-assisted optoelectronic devices such as sensors, molecular reactors and catalysts.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

具有温度辅助光谱发光特性的金属卟啉低聚物的合成与设计

摘要合成了多种不同结构的金属连接卟啉低聚物，并研究了它们对温度的发光敏感性。利用密度泛函理论（DFT）对所得化合物的结构进行了几何优化。通过大环的吡啶基片段与 Pd(II) 和 Pt(II) 阳离子的相互作用形成了配位 Sn(IV)-dipyridyl卟啉四聚体、以及通过吡啶基与 Pd(II) 阳离子配位和 Sn(IV)-卟啉轴向位置上的双螯配体与 Cu(II) 阳离子的双螯结合而形成的八聚体，在 328-383 K 的温度范围内，在 600-650 nm 的波长范围内显示出荧光热灵敏度。在本节中，荧光量子产率（荧光强度）与温度升高的关系是单调的假线性趋势。根据卟啉低聚物的结构，耀斑的范围在 1.5 到 4.5 倍之间。在温度高于 383 K 时，所有以 Pd(II) 为基础获得的卟啉组装体的荧光强度都会下降。同时，它们的结构保持不变。从 Pt(II) 中得到的卟啉四聚体发生了结构重排，变成了一种可能是环甲基化的有机铂化合物，在 493 纳米波长处显示出有效的荧光。研究结果可用于开发新型温度辅助光电设备，如传感器、分子反应器和催化剂。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Russian Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

3.10

自引率

38.10%

发文量

237

审稿时长

3 months

期刊介绍： Russian Journal of Inorganic Chemistry is a monthly periodical that covers the following topics of research: the synthesis and properties of inorganic compounds, coordination compounds, physicochemical analysis of inorganic systems, theoretical inorganic chemistry, physical methods of investigation, chemistry of solutions, inorganic materials, and nanomaterials.