Design for multi-step mechanochromic luminescence property by enhancement of environmental sensitivity in a solid-state emissive boron complex

Saotome, Satoru; Suenaga, Kazumasa; Tanaka, Kazuo; Chujo, Yoshiki

doi:10.1039/c9qm00719a

Cited by 42 publications

(20 citation statements)

References 62 publications

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“…6b). 67 The thienyl-substituted boron ketoiminate 13 formed two polymorphic crystals from THF and methanol solutions that exhibit green and orange emission, respectively. Only the orange-emissive crystals exhibited a two-step MCL.…”

Section: Two-step MCL Of Polymorphic Organic Crystalsmentioning

confidence: 99%

Luminescent polymorphic crystals: mechanoresponsive and multicolor-emissive properties

Ito

2022

CrystEngComm

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Section: Two-step MCL Of Polymorphic Organic Crystalsmentioning

confidence: 99%

Luminescent polymorphic crystals: mechanoresponsive and multicolor-emissive properties

Ito

2022

CrystEngComm

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“…For example, simply by connecting AIE-active boron complexes, AIE-active and solid-state luminescent polymers can be fabricated from heteroatom-containing molecules including boron complexes [ 18 , 19 , 20 , 21 , 22 ]. In particular, since stimuli responsiveness, such as luminochromism as well as intensity changes, was often observed, the series of luminescent sensors can be obtained [ 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. By replacing boron with a different element, such as other group-13 elements, stimuli responsiveness and/or unique luminescent properties were observed [ 30 , 31 , 32 , 33 ].…”

Section: Introductionmentioning

confidence: 99%

Modulation of Properties by Ion Changing Based on Luminescent Ionic Salts Consisting of Spirobi(boron ketoiminate)

et al. 2022

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We report development of luminescent ionic salts consisting of the boron ketoiminate structure, which is one of the robust skeletons for expressing aggregation-induced emission (AIE) properties. From the formation of the boron-centered spiro structure with the ketoiminate ligands, we obtained stable ionic salts with variable anions. Since the ionic salts show Tms below 100 °C, it was shown that these salts can be classified as an ionic liquid. By using PF6 anion, the single crystal—which is applicable for X-ray crystallography—was obtained. According to the optical measurements, it was proposed that electronic interaction should occur through the boron center. Moreover, intense emission was observed both in solution and solid. Finally, we demonstrated that the emission color of the PF6 salt was altered from crystal to amorphous by adding mechanical forces. Based on boron complexation and intrinsic solid-state luminescent characters, we achieved obtainment of emissive ionic materials with environmental responsivity.

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“…[10,41] By enhancing molecular planarity and electronic density of the π-conjugation unit, stimuliresponsivity can be improved. [10] By applying this strategy in the bis-o-carborane-substituted triad molecules, we expected that highly sensitive environment-responsive luminophores can be obtained with luminochromic properties. To evaluate validity of this idea, we designed the thiophene-replaced triad molecules having dual o-carborane units.…”

Section: Introductionmentioning

confidence: 99%

“…[7][8][9] Therefore, specific film-preparation manners are necessary for growing environment-sensitive crystalline form. [10] Success strategies for preparing luminochromic films without restricted manners are to employ alkyl-branched polymers [11,12] and elastomers [13] as a matrix. In the former materials, by altering degree of crystallinity at the side chains, microenvironmental changes around mainchain conjugations followed by luminochromic behaviors are inducible.…”

Section: Introductionmentioning

confidence: 99%

“…According to previous works, it has been reported that environment sensitivity of the πconjugated molecule can be enhanced by replacing benzene to thiophene. [10,41] By enhancing molecular planarity and electronic density of the π-conjugation unit, stimuliresponsivity can be improved. [10] By applying this strategy in the bis-o-carborane-substituted triad molecules, we expected that highly sensitive environment-responsive luminophores can be obtained with luminochromic properties.…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2021

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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 polystyrene. From the optical measurements, it was found that the triad can show solid-state emission and dual-luminescent properties with variable intensity ratios depending on media. From 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 states. We prepared amorphous films containing variable concentrations of the triad with the spin-coating method and investigated optical properties. It was found that intensity ratios were drastically changed by altering the concentration of the triad. By increasing the proportion of the triad, aggregation occurred, and emission color was apparently varied through the changes in intensity ratios of the dual emission property. Based on the aggregationinduced luminochromic property of the triad, thermochromic luminescence was finally realized by heating the amorphous films. The rational design for obtaining thermochromic luminescent amorphous films is illustrated in this paper.

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Design for multi-step mechanochromic luminescence property by enhancement of environmental sensitivity in a solid-state emissive boron complex

Abstract: The solid-state emissive boron complex with multi-step mechanochromic luminescence was designed. The crystalline sample showed gradual changes in luminescent color triggered by scratching. The design concept is illustrated.

Cited by 42 publications

References 62 publications

Luminescent polymorphic crystals: mechanoresponsive and multicolor-emissive properties

Luminescent polymorphic crystals: mechanoresponsive and multicolor-emissive properties

Modulation of Properties by Ion Changing Based on Luminescent Ionic Salts Consisting of Spirobi(boron ketoiminate)

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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