Crystalline-state chemiluminescence reactions of two-fluorophore-linked adamantylideneadamantane 1,2-dioxetane isomers accompanied by solid-to-solid phase transitions

Matsuhashi, Chihiro; Oyama, Hironaga; Uekusa, Hidehiro; Sato‐Tomita, Ayana; Ichiyanagi, Kouhei; Maki, Shôjirô; Hirano, Takashi

doi:10.1039/d2ce00266c

Cited by 6 publications

(3 citation statements)

References 45 publications

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“…Luminescence is a promising property for the in situ observations of phase transitions because it allows the realtime, high-sensitivity detection of the emissive part in a bulk material. [19][20][21][22] Microscopic visualisations of the crystallisation process based on time-course luminescence have been reported previously. [23][24][25][26][27] However, to the best of our knowledge, PCMT has never been studied using luminescence.…”

Section: Introductionmentioning

confidence: 93%

Photoinduced Crystal Melting with Luminescence Evolution Based on Conformational Isomerisation

Komura

Sotome

Miyasaka

et al. 2023

Preprint

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The phenomenon of crystal melting by light irradiation, known as photoinduced crystal-melt transition (PCMT), can dramatically change material properties with high spatiotemporal resolution. However, the diversity of compounds exhibiting PCMT is severely limited, which hampers further functionalisation of PCMT-active materials and the fundamental understandings of PCMT. Here, we report on heteroaromatic 1,2-diketones as the new class of PCMT-active compounds, whose PCMT is based on conformational isomerisation. In particular, one of the diketones demonstrates luminescence evolution prior to crystal melting. Thus, the diketone crystal exhibits dynamic multistep changes in the luminescence colour and intensity during continuous ultraviolet irradiation. This luminescence evolution can be ascribed to the sequential PCMT processes of crystal loosening and conformational isomerisation before macroscopic melting. Single-crystal X-ray structural analysis, thermal analysis, and theoretical calculations of two PCMT-active and one inactive diketones revealed weaker intermolecular interactions for the PCMT-active crystals. In particular, we observed a characteristic packing motif for the PCMT-active crystals, consisting of an ordered layer of diketone core and a disordered layer of triisopropylsilyl moieties. Our results demonstrate the integration of photofunction with PCMT, provide fundamental insights into the melting process of molecular crystals, and will diversify the molecular design of PCMT-active materials beyond classical photochromic scaffolds such as azobenzenes.

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Section: Introductionmentioning

confidence: 93%

Photoinduced Crystal Melting with Luminescence Evolution Based on Conformational Isomerisation

Komura

Sotome

Miyasaka

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Luminescence is a promising property for the in situ observations of phase transitions because it allows the real-time, high-sensitivity detection of the emissive part in a bulk material. 19–22 Microscopic visualisations of the crystallisation process based on time-course luminescence have been reported previously. 23–27 However, to the best of our knowledge, PCLT has never been studied using luminescence.…”

Section: Introductionmentioning

confidence: 96%

Photoinduced crystal melting with luminescence evolution based on conformational isomerisation

et al. 2023

View full text Add to dashboard Cite

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“…22 Luminescence is a promising property for the in situ observations of phase transitions because it allows the real-time, high-sensitivity detection of the emissive part in a bulk material. 1,[23][24][25] Microscopic visualizations of the crystallization process based on time-course luminescence has been reported previously. [26][27][28][29][30] However, to the best of our knowledge, PCMT has never been studied using luminescence.…”

mentioning

confidence: 93%

Light-melting Diketone Crystal with ON-OFF-ON Luminescence Evolution

Komura

Sotome

Miyasaka

et al. 2022

Preprint

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Crystal melting by light irradiation, that is, the phenomenon of photoinduced crystal-melt transition (PCMT), can dramatically change material properties with high spatiotemporal resolution. However, both the process and mechanism of PCMT remain unknown owing to a lack of suitable probes and the poor diversity of compounds exhibiting PCMT. Here, we report the first instance of PCMT with luminescence evolution. We show that a heteroaromatic 1,2-diketone crystal exhibits ON-OFF-ON luminescence changes under continuous ultraviolet irradiation, which can be ascribed to the sequential PCMT processes of crystal loosening and conformational isomerization before macroscopic melting. Single-crystal X-ray structural analysis, thermal analysis, and theoretical calculations of three diketones revealed that weak intermolecular interactions and the presence of a disordered layer in the crystal are essential for PCMT. Our results provide fundamental insights into the melting process of molecular crystals and should aid the molecular design of PCMT-active materials that are based on emissive compounds, as opposed to the classical molecular designing based on nonemissive photochromic scaffolds such as azobenzenes.

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Crystalline-state chemiluminescence reactions of two-fluorophore-linked adamantylideneadamantane 1,2-dioxetane isomers accompanied by solid-to-solid phase transitions

Abstract: Structural isomers (cis-syn, cis-anti and trans isomers) of an adamantylideneadamantane 1,2-dioxetane having two fluorophore side chains were prepared and investigated their chemiluminescence (CL) properties in the crystalline state. Real-time monitoring...

Cited by 6 publications

References 45 publications

Photoinduced Crystal Melting with Luminescence Evolution Based on Conformational Isomerisation

Photoinduced Crystal Melting with Luminescence Evolution Based on Conformational Isomerisation

Photoinduced crystal melting with luminescence evolution based on conformational isomerisation

Light-melting Diketone Crystal with ON-OFF-ON Luminescence Evolution

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