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Molecular design and application of luminescent materials composed of group 13 elements with an aggregation-induced emission property

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National Science Review 2021年第6期8卷 80-93页

作者： Shunichiro Ito Masayuki Gon Kazuo Tanaka yoshiki chujo Department of Polymer Chemistry Graduate School of EngineeringKyoto University

Complexation of π-conjugated ligands by metal or semimetal ions leads to the enhancement of the planarity and rigidity of π-conjugated systems. Boron, especially, has played a central role in the design of luminescent main-group complexes. However, these complexes still suffer the disadvantage of aggregation-caused quenching as well as typical organic fluorophores. It has recently been reported that some types of boron complexes exhibit the aggregation-induced emission(AIE) property. Moreover, AIE behavior from complexes and organometallic compounds composed of the other group 13 elements, such as aluminum and gallium, has emerged in this decade. These observations greatly encourage us to develop advanced functional materials based on the group 13 elements. Indeed, recent research has demonstrated that these classes of materials are potentially versatile scaffolds for constructing chromic luminophores,efficiently emissive π-conjugated polymers and so on. This review mainly describes AIE-active group 13 complexes with four-coordinate structures and their application as photo-functional materials. Proposed mechanisms of the origins of AIE behavior are briefly discussed.

关键词： aggregation-induced emission crystallization-induced emission chromism conjugated polymer group 13

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Positive Luminescent Sensor for Aerobic Conditions Based on Polyhedral Oligomeric Silsesquioxane Networks

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Chemical Research in Chinese Universities 2021年第1期37卷 162-165页

作者： Kazumasa SUENAGA Kazuo TANAKA yoshiki chujo Department of Polymer Chemistry Graduate School of EngineeringKyoto UniversityKatsuraNishikyo-kuKyoto615-8510Japan

There are numerous numbers of hypoxia-selective luminescent probes based on oxygen quenching of *** show a unique design for luminescent probes to detect hyperoxia utilizing hybrid networks consisting of aggregation-induced emission(AIE)-active dyes and disulfide *** the initial state,emission from the AIE-active dyes is inducible by suppressing energy-consumable intramolecular motions in the hybrid matrices,while the decrease in intensity was detected by releasing molecular motions corresponded to bond scission at the disulfide ***,it was shown that this process selectively proceeds in *** a result,positive luminescent signals were obtained in hyperoxia.

关键词： Polyhedral oligomeric silsesquioxane(POSS) Network polymer Hypoxia Luminescent probe

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Comparison of luminescent properties of helicene-like bibenzothiophenes with o-carborane and 5,6-dicarba-nidodecaborane

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Science China Chemistry 2018年第8期61卷 940-946页

作者： Kenta Nishino Kazushi Hashimoto Kazuo Tanaka Yasuhiro Morisaki yoshiki chujo Department of Polymer Chemistry Graduate School of Engineering Kyoto University Department of Applied Chemistry for Environment School of Science and Technology Kwansei Gakuin University

This article describes comparison of the anchoring effect on electronic properties of the helicene-like bibenzothiophene between o-carborane and 5,6-dicarba-nido-decaborane. The o-carborane and nido-decaborane-fused bibenzothiophenes were simultaneously obtained in the same reaction and successfully isolated. Initially, the X-ray single crystal analysis revealed that the helicene-like distorted structure was realized in the nido-decaborane-fused bibenzothiophene. From optical measurements in the solution state, distinct different characteristics depending on the type of anchors were observed. It was summarized that the absorption and luminescent properties originated from weak π-conjugation at the bibenzothiophene moiety in the o-carboranefused compound were obtained, whereas robust π-conjugation and significant emission from the intramolecular charge transfer state were detected from the nido-decaborane-fused compound. These data can be explained by the theoretical results that π-conjugation was restrictedly developed within the bibenzothiophene moiety in frontier orbitals of the o-carborane-fused compound. In contrast, π-conjugation can be constructed even through the distorted bibenzothiophene because of the nido-decaborane unit. Moreover, the intramolecular charge transfer state should be realized because of electronic interaction involving the nido-decaborane unit in the excited state. Furthermore, it was demonstrated that the nido-decaborane-fused compound possessed solid-state emission and mechanochromic luminescent properties. The π-conjugation on the distorted structure supported by the nido-decaborane anchor should play a significant role in suppressing aggregation-caused quenching followed by presenting solid-state emission with stimuli responsiveness.

关键词： carborane helicene mechanochromism aggregation-induced emission

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Rational design for thermochromic luminescence in amorphous polystyrene films with bis-o-carborane-substituted enhanced conjugated molecule having aggregation-induced luminochromism

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Aggregate 2021年第5期2卷 171-178页

作者： Keisuke Wada Kazushi Hashimoto Junki Ochi Kazuo Tanaka yoshiki chujo Department of Polymer Chemistry Graduate School of EngineeringKyoto University KatsuraNishikyo-kuKyotoJapan

We designed the triad molecule,bis-o-carborane-substituted bis(thienylethynyl)benzene,as a filler for realizing thermochromic luminescent behaviors based on conventional polymer films,such as *** the optical measurements,it was found that the triad can show solid-state emission and dual-luminescent properties with variable intensity ratios depending on *** the mechanistic studies including the experiments with the methyl-substituted model compound,it was revealed that dual emission should be originated from the locally excited and twisted intramolecular charge transfer states,and the latter emission band is significantly enhanced in the solid *** prepared amorphous films containing variable concentrations of the triad with the spin-coating method and investigated optical *** was found that intensity ratios were drastically changed by altering the concentration of the *** increasing the proportion of the triad,aggregation occurred,and emission color was apparently varied through the changes in intensity ratios of the dual emission *** on the aggregationinduced luminochromic property of the triad,thermochromic luminescence was finally realized by heating the amorphous *** rational design for obtaining thermochromic luminescent amorphous films is illustrated in this paper.

关键词： carborane luminescence polystyrene thermochromism

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Organic-inorganic Polymer Nano-hybrids Based on Sol-gel Reaction

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复旦学报（自然科学版） 2007年第5期46卷 556-页

作者： yoshiki chujo Department of Polymer Chemistry Kyoto University

1 Results Nano-ordered composite materials consisting of organic polymers and inorganic materials have been attracting attention for the purpose of the creation of high-performance or high-functional polymeric materials. Especially,the word of "polymer hybrid" claims the blends of organic and inorganic components at nano-level dispersion. By using this idea,an enhancement of mechanical strength of organic polymers with silica particles is *** transparency of this material is another important ...

关键词： polymer hybrids nano-materials sol-gel reaction

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