Transformation of sulfur to organic-inorganic hybrids employed by networks and their application for the modulation of refractive indices

Tanaka, Kazuo; Yamane, Honami; Mitamura, Koji; Watase, Seiji; Matsukawa, Kimihiro; Chujo, Yoshiki

doi:10.1002/pola.27274

Cited by 32 publications

(20 citation statements)

References 52 publications

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“…In previous studies, it was shown that POSS derivatives could suppress molecular motions of surrounding molecules through covalent or noncovalent bonds . As a result, thermal stabilities of the materials, including ion pairs directly connected to POSS and polymers with interactions with POSS, can be improved. To apply this stabilization effect of POSS to the preservation of disordered states of fluorescent molecules from crystallization after adding mechanical stresses, POSS octasubstituted with boron ketoiminate (M‐POSS; Scheme ) was designed.…”

Section: Resultsmentioning

confidence: 99%

Heat‐Resistant Mechanoluminescent Chromism of the Hybrid Molecule Based on Boron Ketoiminate Modified Octasubstituted Polyhedral Oligomeric Silsesquioxane

Suenaga

Tanaka

Chujo

2016

Chemistry A European J

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The development of a heat-resistant mechanoluminescent chromic (MLC) dye based on an organic-inorganic hybrid molecular scaffold is reported. Luminescent organoboron complexes were introduced into polyhedral oligomeric silsesquioxane (POSS) at each vertex through the rigid linker structure in the Suzuki-Miyaura cross-coupling reaction. From optical measurements, it was found that the crystalline state of the modified POSS showed orange emission. By adding mechanical forces to the sample, regular structures collapsed. Correspondingly, the emission color turned to yellow. Interestingly, the yellow-emissive amorphous state can be preserved during heating. By radially distributing luminescent chromophores on the rigid cube, both optical and thermal properties can be modulated to realize heat- resistant MLC behavior. POSS can contribute not only to expressing the MLC behavior, but also to improving thermal stability in the amorphous state. This is the first example, to the best of our knowledge, to offer the rational design of a heat-resistant MLC material.

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Section: Resultsmentioning

confidence: 99%

Heat‐Resistant Mechanoluminescent Chromism of the Hybrid Molecule Based on Boron Ketoiminate Modified Octasubstituted Polyhedral Oligomeric Silsesquioxane

Suenaga

Tanaka

Chujo

2016

Chemistry A European J

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“…It was also shown that lanthanoid cations can be efficiently captured in the presence of the appropriate ligand structures [ 50 ]. By applying the assembling effect of SSQ, it can be expected that an additional enhancement to RI values is expected without losses of Abbe numbers [ 27 , 28 ]. As a metal cation for loading onto the SSQ matrices, we selected the series of lanthanoid ions, which have been used as an additive for increasing RIs of polymer films.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, Kudo et al reported that the RI values of the polymer films can be lifted up by simply connecting the polymer chain ends with the rigid building blocks [ 23 , 24 , 25 , 26 ,]. Based on this finding, we also prepared the SSQ networks composed of oligosulfide linkers and detected the increase in the RI of conventional polymer films by blending these sulfur-containing SSQ networks without enlarging wavelength dependency of light refraction represented by an Abbe number [ 27 ]. More recently, similar increasing effects on RI without losses of Abbe numbers were also observed with the hybrids containing halogenated SSQ [ 28 ].…”

Section: Introductionmentioning

confidence: 99%

High Refractive-Index Hybrids Consisting of Water-Soluble Matrices with Bipyridine-Modified Polyhedral Oligomeric Silsesquioxane and Lanthanoid Cations

et al. 2020

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We report high refractive-index (RI) films composed of polyhedral oligomeric silsesquioxane (SSQ) matrices and various lanthanoid cations. The SSQ matrices were constructed from octaammonium SSQ by connecting with bipyridine dicarboxylic acid, which is expected to capture cations. By modulating the feed ratio between SSQ and dicarboxylic acid, the series of the SSQ matrices were obtained with variable cross-linking ratios among the SSQ units. Thin transparent films were able to be prepared through the drop-casting method with the aqueous mixtures containing SSQ matrices and various kinds of lanthanoid salts up to 40 wt %. From RI measurements, it was revealed that the increase of the amount of the metal ion can significantly lift up the RI values. In particular, critical losses of Abbe numbers, which theoretically have the trade-off relationship toward increases in RI values, were hardly detected. This effect could be obtained by cation assembly in local spots that are assisted by SSQ.

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“…22,23 Furthermore, by modifying POSS, the trade-off relationships were maintained between multiple competing functions in the materials. [24][25][26][27][28] In this part, the preparation of 'designable hybrids' by utilizing modified POSS and the material properties are described.…”

Section: Poss Element-blocks For Realizing Designable Hybridsmentioning

confidence: 99%

Recent progress in the development of advanced element-block materials

Gon

Tanaka

Chujo

2017

Polym J

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140

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An element-block is defined as a minimum functional unit composed of heteroatoms. The concept of 'element-block material' for designing advanced materials was proposed in 2015. In this review, the recent progress in material designs based on this concept is described. From our research, several element-blocks as representative examples are selected, and their roles in each material are explained. Initially, research on the development of 'designable hybrids' by employing polyhedral oligomeric silsesquioxane (POSS) is illustrated. Multiple functions of hybrids composed of modified POSS and the significant roles of POSS in bio-related polymeric materials for solving critical problems in conventional 19 F MR probes and for realizing new sensing technologies are demonstrated. Next, solid-state luminescent materials containing o-carborane and group 13 element-blocks are discussed. The materials' highly efficient emission in the solid state and their origins are explained. Furthermore, stimuliresponsive luminescent chromism is summarized. The sensing mechanisms and the application of these materials as sensors are presented in this study. In the last part, we mention optically active element-blocks containing chiral P-stereogenic phosphorus. In this review, the characteristics originating from each element-block are explained.

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Transformation of sulfur to organic-inorganic hybrids employed by networks and their application for the modulation of refractive indices

Cited by 32 publications

References 52 publications

Heat‐Resistant Mechanoluminescent Chromism of the Hybrid Molecule Based on Boron Ketoiminate Modified Octasubstituted Polyhedral Oligomeric Silsesquioxane

Heat‐Resistant Mechanoluminescent Chromism of the Hybrid Molecule Based on Boron Ketoiminate Modified Octasubstituted Polyhedral Oligomeric Silsesquioxane

High Refractive-Index Hybrids Consisting of Water-Soluble Matrices with Bipyridine-Modified Polyhedral Oligomeric Silsesquioxane and Lanthanoid Cations

Recent progress in the development of advanced element-block materials

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