A facile and versatile approach to efficient enhancement of solid-state luminescence by organic–inorganic hybrid salts

Tohnai, Norimitsu; Sugino, Misa; Araki, Yusuke; Hatanaka, Kenichi; Hisaki, Ichiro; Miyata, Mikiji

doi:10.1039/c3dt51422f

Cited by 11 publications

(6 citation statements)

References 24 publications

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“…Static disorder, i.e., when a molecule is disordered over several fixed positions with different occupancies in crystal, may produce several different environments of a key molecule responsible for the desired property of the crystal. As some molecular properties, e.g., luminescence, − are environmentally sensitive, several different environments may give rise to several different values of the same property. By changing the population of each environment, it seems possible to tune the average value of the property in the same crystal, by analogy with the mixed-lanthanide metal–organic complex, where variation of the Gd:Eu:Tb ratio tunes complex emission within the full-color region.…”

Section: Introductionmentioning

confidence: 99%

Disorder for the Sake of Order

Тафеенко

Gurskiy

2016

Crystal Growth & Design

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Crystal structure analysis of two N,N-dimethylanilinium 3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrole-2-olate (DMA+_HA–) polymorphs (α, β) allowed us to conclude that a degree of disorder in crystal is a constant characteristic of the polymorph. A change in the degree of disorder in the crystal requires a change in the crystal phase. The disorder effect on solid-state luminescence of α, β polymorphs is presented.

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Section: Introductionmentioning

confidence: 99%

Disorder for the Sake of Order

Тафеенко

Gurskiy

2016

Crystal Growth & Design

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“…The cationic fluorogens are usually designed with complex and flexible structures to against the strong dipole-dipole interactions, which open the non-radiation decay channels and thus quench the solid-state luminescence. The changes of the anions would also greatly influence the emission in aggregation of organic salts because the strength of electrostatic attraction between cationic and anionic species and steric hindrance may deeply affect the molecular packing in aggregation4445464748495051. Bhattacharya, et al .…”

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confidence: 99%

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Zhang

Kong

et al. 2016

Sci Rep

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Molecular packing arrangements play a key role in dominating the photophysical properties of luminophores in aggregated state but fine control of the molecular packing is a great challenge. This article describes a unique cyano substituted styrene pyridinium with interesting solid-state fluorescence that can be finely tuned by simple change of counteranions. The dilute solutions of the organic salts (PyCl, PyNO3, PyOTs and PyPh4B) exhibit very weak fluorescence. The crystals of the organic salts (PyCl, PyNO3, and PyOTs) show much enhanced fluorescence compared with their dilute solutions. It is interesting that the emissions changed from bluish-green to deep-blue and fluorescence quantum yields increase from 2.5% to 13.1% with the increasing of steric hindrance of the anions from chloridion, nitrate, to p-toluenesulfonate. Crystal and DFT studies reveal that the enhanced fluorescence is ascribed to the formation of dimers and bigger anions induce larger molecular separation in dimers. Tetraphenylboron anion with very large steric hindrance impedes the formation of dimers and thus results in non-fluorescent salt (PyPh4B). Meanwhile, this unique dimeric packing endows the crystal of PyNO3 with anisotropic fluorescence.

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“…The peak at 460 nm on the excitation spectrum of 2 c crystal in Figure a is derived from the formation of BBFPy skeleton dimer in the ground state. These results indicate that unsubstituted BBFPy 2 c molecules strongly interacted with each other in the ground state to cause the red‐shifted and broadened luminescence ,…”

Section: Resultsmentioning

confidence: 87%

“…In unsubstituted BBFPy 2 c crystal, there are strong interactions between BBFPy skeletons in the ground state, leading to formation of a ground state dimer. Consequently, the largely red‐shifted and broadened emission was from the ground state dimer ,. The ground state interactions in the BBFPy crystal were also suggested by the pale yellow color of the crystal, whereas the other crystals were colorless.…”

Section: Resultsmentioning

confidence: 93%

Effect of Substitution Pattern of tert‐Butyl Groups in a Bisbenzofuropyrazine Core π‐System on Optical Properties: Unique Mechanochromic Fluorescence Behavior

Nakamura

Tohnai

Nishii³

et al. 2018

ChemPhotoChem

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Bisbenzofuro[2,3‐b : 2′,3′‐e]pyrazine (BBFPy) and its 2,8‐ and 3,9‐di(tert‐butyl)‐substituted derivatives (2 a and 2 b) were synthesized by palladium‐catalyzed intramolecular direct arylation as the key step. The effect of introduction of two tert‐butyl groups to the BBFPy core at the different positions on the fluorescent properties was then investigated. The tert‐butyl groups not only enhance the tractability with increasing solubility, but also induce different crystal‐packing patterns as anticipated. The compounds 2 a and 2 b show relatively strong blue fluorescence in both the solution and solid state. The 2,8‐isomer 2 a specifically exhibits a unique mechanochromism in the solid state; 2 a exhibits two crystalline forms, both of which show green fluorescence by grinding, while different self‐recovering fluorescence patterns between them are observed by standing. The intriguing mechanochromism is rationally interpreted in terms of molecular arrangements determined by X‐ray crystallography.

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A facile and versatile approach to efficient enhancement of solid-state luminescence by organic–inorganic hybrid salts

Cited by 11 publications

References 24 publications

Disorder for the Sake of Order

Disorder for the Sake of Order

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Effect of Substitution Pattern of tert‐Butyl Groups in a Bisbenzofuropyrazine Core π‐System on Optical Properties: Unique Mechanochromic Fluorescence Behavior

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