Different photochemical behavior of bis(biphenyl)ethylenes and ethenes in solution and in the solid-state: Structurally controlled Z/E-photoisomerization in the solid-state

Fengqiang, Zhu; Motoyoshiya, Jiro; Nishii, Yoshinori; Aoyama, Hiromu; Kakehi, Akikazu; Shiro, Motoo

doi:10.1016/j.jphotochem.2006.03.022

Cited by 5 publications

(4 citation statements)

References 23 publications

(24 reference statements)

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“…First, pure ( E )-CN-MBE powders were irradiated with 365 nm UV light at room temperature to affect the E to Z isomerization process up to 1 day, and it was found that no change in 1 H NMR spectra was observed before and after light illumination. This result indicates that ( E )-CN-MBE keeps its molecular conformation even upon long exposure of UV light because ( E )-CN-MBE molecules are densely packed and confined with strong π–π intermolecular interactions in the solid state which presumably requires a high thermal activation energy for E to Z isomerization . However, it was found that the E to Z isomerization process of ( E )-CN-MBE efficiently occurs in the LC mesophase state ( T = 224–230 °C) under UV irradiation (λ irra = 365 nm).…”

Section: Resultsmentioning

confidence: 98%

High-Contrast On/Off Fluorescence Switching via Reversible E–Z Isomerization of Diphenylstilbene Containing the α-Cyanostilbenic Moiety

et al. 2013

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Fluorescence switching or modulation of π-conjugated molecules is of great interest in the area of optoelectronic materials science and technology because of their promising applications. However, the “concentration fluorescence quenching” problems commonly associated with conventional π-conjugated molecules in the solid state were occasionally an obstacle to use of π-conjugated molecules in high-contrast memory storage devices. We designed and synthesized a novel class of fluorescence switching π-conjugated molecule, (Z)-CN-MBE, that exhibits a reversible photo/thermal E/Z isomerization process, accompanied by a remarkable fluorescence on/off switching in the solid state. This may provide a promising way to construct high-contrast optical binary memory storage devices. (Z)-CN-MBE is virtually nonfluorescent but exhibits an extraordinary Z to E isomerization upon external light/thermal stimuli even in the solid state with a concomitant drastic fluorescence enhancement owing to the unique “aggregation-induced enhanced emission” (AIEE)’ phenomenon of its trans isomer.

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Section: Resultsmentioning

confidence: 98%

High-Contrast On/Off Fluorescence Switching via Reversible E–Z Isomerization of Diphenylstilbene Containing the α-Cyanostilbenic Moiety

et al. 2013

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“…Their UV/Vis spectra are similar in shape, with maximum absorption wavelengths ( λ max ) of 335 nm and 337 nm for (oP 4 ) 3 and (oP 6 ) 3 , respectively. These spectra are a close match to that of ( E )‐4,4'‐diphenylstilbene ( λ max = 342 nm),, which represents a single side of each macrocycle excluding conjugation through the o ‐phenylene moieties. Curiously, despite the structural and spectral similarities, the macrocycles show significantly different absorptivities ( ε ), with that of (oP 6 ) 3 approximately double that of (oP 4 ) 3 [(7.9 ± 0.6) × 10 4 m – 1 vs. (3.8 ± 0.3) × 10 4 m – 1 ].…”

Section: Resultsmentioning

confidence: 56%

ortho‐Phenylene‐Based Macrocyclic Hydrocarbons Assembled Using Olefin Metathesis

et al. 2020

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While many foldamer systems reliably fold into well‐defined secondary structures, higher order structure remains a challenge. A simple strategy for the organization of folded subunits in space is to link them together within a macrocycle. Previous work has shown that o‐phenylenes can be co‐assembled with rod‐shaped linkers into twisted macrocycles, showing an interesting synergy between folding and thermodynamically controlled macrocyclization. In these systems the foldamer units were largely decoupled from each other both conformationally and electronically. Here, we show that hydrocarbon macrocycles, with very short ethenylene linkers, can be assembled from o‐phenylenes using olefin metathesis. Characterization by NMR spectroscopy, X‐ray crystallography, and ab initio calculations shows that the products are approximately triangular trimer macrocycles with helical o‐phenylene corners in a heterochiral configuration. Their photophysics are dominated by the 4,4'‐diphenylstilbene moieties, the longest conjugated segments, with further conjugation broken by the twisting of the o‐phenylenes.

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“…Their UV-vis spectra are similar in shape, with maximum absorption wavelengths (λ max ) of 335 nm and 337 nm for (oP 4 ) 3 and (oP 6 ) 3 , respectively. These spectra are a close match to that of (E)-4,4 -diphenylstilbene (λ max = 342 nm), 43,44 which represents a single side of each macrocycle excluding conjugation through the o-phenylene moieties. Curiously, despite the structural and spectral similarities, the macrocycles show significantly different absorptivities, with that of (oP 6 ) 3 approximately double that of (oP 4 ) 3 ((7.9 ± 0.6) × 10 4 M −1 vs (3.8 ± 0.3) × 10 4 M −1 ).…”

Section: Structural Analysis Of (Op 6 )mentioning

confidence: 56%

Ortho-Phenylene-Based Macrocyclic Hydrocarbons Assembled Using Oleﬁn Metathesis

Kirinda¹,

Schrage²,

Ziegler³

et al. 2020

Preprint

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While many foldamer systems reliably fold into well-defined secondary structures, higher order structure remains a challenge. A simple strategy for the organization of folded subunits in space is to link them together within a macrocycle. Previous work has shown that o-phenylenes can be co-assembled with rod-shaped linkers into twisted macrocycles, showing an interesting synergy between folding and thermodynamically controlled macrocyclization. In these systems the foldamer units were largely decoupled from each other both conformationally and electronically. Here, we show that hydrocarbon macrocycles, with very short ethenylene linkers, can be assembled from o-phenylenes using olefin metathesis. Characterization by NMR spectroscopy, X-ray crystallography, and ab initio calculations shows that the products are approximately triangular [3+3] macrocycles with helical o-phenylene corners in a heterochiral configuration. Their photophysics are dominated by the 4,4′-diphenylstilbene moieties, the longest conjugated segments, with further conjugation broken by the twisting of the o-phenylenes.

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Different photochemical behavior of bis(biphenyl)ethylenes and ethenes in solution and in the solid-state: Structurally controlled Z/E-photoisomerization in the solid-state

Cited by 5 publications

References 23 publications

High-Contrast On/Off Fluorescence Switching via Reversible E–Z Isomerization of Diphenylstilbene Containing the α-Cyanostilbenic Moiety

High-Contrast On/Off Fluorescence Switching via Reversible E–Z Isomerization of Diphenylstilbene Containing the α-Cyanostilbenic Moiety

ortho‐Phenylene‐Based Macrocyclic Hydrocarbons Assembled Using Olefin Metathesis

Ortho-Phenylene-Based Macrocyclic Hydrocarbons Assembled Using Oleﬁn Metathesis

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