Toushique Ahmed, Amit Chakraborty and Sujoy Baitalik*,
{"title":"与 Ln(六氟乙酰丙酮)3 核心配位的基于 Terpyridyl-Imidazole 的配体:溶液和 PMMA 薄膜中的合成、结构表征、发光特性和热感应行为","authors":"Toushique Ahmed, Amit Chakraborty and Sujoy Baitalik*, ","doi":"10.1021/acs.inorgchem.4c01132","DOIUrl":null,"url":null,"abstract":"<p >A new array of ternary lanthanide complexes of the form [Ln(hfa)<sub>3</sub>(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = La<sup>III</sup> (<b>1</b>), Eu<sup>III</sup> (<b>2</b>), Sm<sup>III</sup> (<b>3</b>), and Tb<sup>III</sup> (<b>4</b>); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-<i>d</i>]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for La<sup>III</sup>; almost complete energy transfer for Eu<sup>III</sup>; very little energy transfer for Sm<sup>III</sup>, while reverse energy transfer in the case of Tb<sup>III</sup>. In addition, the Eu<sup>III</sup>-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set–reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 24","pages":"11279–11295"},"PeriodicalIF":4.7000,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film\",\"authors\":\"Toushique Ahmed, Amit Chakraborty and Sujoy Baitalik*, \",\"doi\":\"10.1021/acs.inorgchem.4c01132\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A new array of ternary lanthanide complexes of the form [Ln(hfa)<sub>3</sub>(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = La<sup>III</sup> (<b>1</b>), Eu<sup>III</sup> (<b>2</b>), Sm<sup>III</sup> (<b>3</b>), and Tb<sup>III</sup> (<b>4</b>); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-<i>d</i>]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for La<sup>III</sup>; almost complete energy transfer for Eu<sup>III</sup>; very little energy transfer for Sm<sup>III</sup>, while reverse energy transfer in the case of Tb<sup>III</sup>. In addition, the Eu<sup>III</sup>-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set–reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"63 24\",\"pages\":\"11279–11295\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2024-06-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c01132\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c01132","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film
A new array of ternary lanthanide complexes of the form [Ln(hfa)3(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = LaIII (1), EuIII (2), SmIII (3), and TbIII (4); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-d]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for LaIII; almost complete energy transfer for EuIII; very little energy transfer for SmIII, while reverse energy transfer in the case of TbIII. In addition, the EuIII-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set–reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.