End-to-end communication in a linear supermolecule with a BOPHY centre and <i>N</i>,<i>N</i>-dimethylanilino-based terminals

Woodford, Owen J.; Stachelek, Patrycja; Ziessel, Raymond; Algoazy, Nawaf; Knight, Julian G.; Harriman, Anthony

doi:10.1039/c7nj04654e

Cited by 10 publications

(4 citation statements)

References 67 publications

(47 reference statements)

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“…[29] Interestingly, when studying compound 32, Harriman et al report no through-bond electronic coupling between the two aniline N atoms, both for protonation and oxidation, although the system is fully conjugated. [30] Polyethylene glycol substituted derivative 33 was synthesized in 65% yield as a proof for double substitution. [25] Organometallic BOPHY 34 was synthesized in a low yield of 4%.…”

Section: Halogenation Of Bophymentioning

confidence: 99%

The BOPHY fluorophore with double boron chelation: Synthesis and spectroscopy

Boodts

Fron

Hofkens

et al. 2018

Coordination Chemistry Reviews

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Section: Halogenation Of Bophymentioning

confidence: 99%

The BOPHY fluorophore with double boron chelation: Synthesis and spectroscopy

Boodts

Fron

Hofkens

et al. 2018

Coordination Chemistry Reviews

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“…Radiationless decay of the excited state becomes progressively more significant with increasing polarity of the solvent. This situation is reminiscent of that reported recently for a styryl‐BOPHY derivative bearing terminal N,N‐dimethylanilino groups . Here, intramolecular charge‐transfer interactions involving the terminal donors and the central BOPHY acceptor were invoked to explain the large solvent effect recorded for the fluorescence properties.…”

Section: Resultsmentioning

confidence: 53%

Photofading of an Extended BOPHY Chromophore Dispersed in Poly(methyl methacrylate) as a Chemical Actinometer

2018

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The target compound is a member of the symmetric pyrrole-BF 2 family, known as BOPHY, which has been equipped with 3,8styryl groups that push the absorption maximum to lower energy. To assist solubility and facile dispersion in plastic films, poly(ethylene glycol) chains are added to the styryl groups. The photophysical properties are somewhat sensitive to changes in solvent polarity and temperature due to the imposition of weak, intramolecular charge-transfer character. The chromophore bleaches under white-light illumination to form an intermediate species that absorbs and emits at higher energy. This species is believed to be a BOPHY unit with one styryl arm removed from the conjugation path. The intermediate is quite resistant to photobleaching but does fade on prolonged illumination. The kinetics associated with photobleaching in poly(methyl methacrylate) films allow development of a simple model that can be used to establish a robust chemical actinometer for recording exposure to sunlight. Similar photofading behaviour is observed in polar solution, where self-catalysis is observed, with the overall kinetics depending on the nature of the solvent.[a] O.

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“…Within this environment, charge-transfer between adjacent units can be favoured by some forms of dipole-dipole alignment, enabling a deactivation route that BOPHY dyes do not normally show intramolecularly, despite their relatively high transition dipole moments. ( Woodford et al, 2018 ; Hupfer et al, 2021 ).…”

Section: Resultsmentioning

confidence: 99%

Hybridising inorganic materials with fluorescent BOPHY dyes: A structural and optical comparative study

et al. 2022

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This study presents the design and characterization of new monochromatic light-harvesting systems based on inorganic porous materials hybridized with organic dye molecules within their structure. A new fluorescent BOPHY dye was prepared, characterized optically and used as both reference and synthetic precursor for two alkoxysilane derivatives that were incorporated separately within a silica structure. The dyes, one bearing one alkoxysilane group and the other one two, were co-condensed with tetraethyl orthosilicate to form a hybrid organo-silica framework, where they are found at specific locations. The structure of the new materials was analysed by powder XRD and TEM, which confirmed the presence of the hexagonal pore arrangement typical of mesoporous MCM-41 silica particles. The steady-state and time-resolved analysis showed that the particles where the dyes are most dispersed within the framework retain the highest fluorescence quantum yield, up to 0.63, in the green-yellow region of the visible spectrum. On the other hand, increasing the content of BOPHY units in the solid matrix seem to favour non-radiative deactivation pathways and aggregation phenomena, which lower the efficiency of light emission. The materials also exhibit interesting properties, such as a dual excited-state decay and fluorescence anisotropy. The short fluorescence lifetime, about 2 ns, matches the typical singlet lifetime of BOPHY dyes, whereas the long component, up to 20 ns, is attributed to delayed fluorescence, which could take place via charge recombination. Optical anisotropy experiments revealed that all materials show polarised light emission to a significant extent and, for most samples, it was also possible to determine a polarisation transfer decay trace, from 400 to 800 ps This is ascribed to the occurrence of energy migration between neighbouring dye units within the silica structure.

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End-to-end communication in a linear supermolecule with a BOPHY centre and N,N-dimethylanilino-based terminals

Abstract: Long-range electrostatic interactions are sufficient to cause sequential ionization of the terminal groups in a BOPHY-based supermolecule.

Cited by 10 publications

References 67 publications

The BOPHY fluorophore with double boron chelation: Synthesis and spectroscopy

The BOPHY fluorophore with double boron chelation: Synthesis and spectroscopy

Photofading of an Extended BOPHY Chromophore Dispersed in Poly(methyl methacrylate) as a Chemical Actinometer

Hybridising inorganic materials with fluorescent BOPHY dyes: A structural and optical comparative study

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