Synthetic Emission Tuning of Carborane-Containing Poly(dihexylfluorene)s

Martin, Kara L.; Smith, Jessalyn; Young, Elizabeth R.; Carter, Kenneth R.

doi:10.1021/acs.macromol.9b01325

Cited by 28 publications

(24 citation statements)

References 55 publications

(84 reference statements)

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“…Given the previous reports on the improved emissive behavior of carborane‐fluorophore conjugates upon aggregation, [6,7c–j] we also investigated the optical properties of 1 and 2 in the solid state, which were compared to those of reference PDI dye 7 . As previously reported for thin films of symmetric perylenediimide fluorophores bearing branched alkyl side chains, [37] large differences were observed when optically characterizing 7 as a solid powder relative to solution.…”

Section: Resultsmentioning

confidence: 99%

“…The emission from these AIE‐active, CT‐based carborane‐emitter conjugates is sensitive to external stimuli that alter molecular packing (e.g. mechanical forces, temperature, chemical environment), and can be used for the preparation of smart materials [7c–j] . However, attempts to provide further functionality to these systems by reversibly switching the electronic communication between fluorophores and boron clusters have not been reported.…”

Section: Introductionmentioning

confidence: 99%

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Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Parejo

Chaari

Santiago

et al. 2020

Chemistry A European J

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Icosahedral metallacarboranes are q-shaped anionic molecules in which two icosahedra share one vertex that is am etal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C 2 B 9 H 11) 2 ] À , whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes[ Co(C 2 B 9 H 11) 2 ] À very appealingt o participatei ne lectron-transfer processes. In this work, [Co(C 2 B 9 H 11) 2 ] À is tethered to ap erylenediimided ye to produce the first examples of switchable luminescentm olecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C 2 B 9 H 11) 2 ] À with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systemsb ased on conjugates of perylendiimides with ferrocene. Remarkably,t hey can form gels by treatment with appropriate mixtureso fo rganic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimidec onjugates into 1D nanostructures. The interplay between dye p-stackinga nd metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangementi nt hese materials, which for one of the compoundsp repared allows preserving the luminescent behavior in the gel state.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Parejo

Chaari

Santiago

et al. 2020

Chemistry A European J

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“…Carter et al. reported a series of carborane‐containing polyfluorenes 25 – 27 . Optoelectronic devices were fabricated with the emissive conjugated network involving o ‐carborane for the first time.…”

Section: Aggregation‐induced Emissionmentioning

confidence: 99%

“…It was demonstrated that the carborane cage is responsible for the improvement of charge carrier mobility by an order of magnitude . In another paper, the emission color was tuned in a wide wavelength range by changing the introduction rate of the carborane unit . Moreover, 25 showed vapochromic properties.…”

Section: Aggregation‐induced Emissionmentioning

confidence: 99%

Recent Progress in the Development of Solid‐State Luminescent o‐Carboranes with Stimuli Responsivity

2020

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o‐Carborane, a cluster compound containing boron and adjacent carbon atoms, displays intriguing luminescent properties. Recently, compounds containing o‐carborane units were found to show suppressed aggregation‐induced quenching and intense solid‐state emission; they also show potential for the development of stimuli‐responsive luminochromic materials. In this Minireview, we introduce three kinds of fundamental photochemical properties: aggregation‐induced emission, twisted intramolecular charge transfer in crystals, and environment‐sensitive excimer formation in solids. Based on these properties, several types of luminochromism, such as thermos‐, vapo‐, and mechanochromism, have been discovered. Based mainly on results from recent studies, we illustrate these mechanisms as well as unique luminescent behaviors of o‐carborane derivatives.

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“…Owing to these features, such o -carboranyl compounds have recently been proposed as promising optoelectronic materials for organic light emitting diodes [ 7 , 8 ] and organic thin-film transistors [ 9 , 10 ]. The intriguing photophysical properties of o -carboranyl luminophores originate from the electronic donor‒acceptor (D–A) dyad formed by combining a π-conjugated aromatic organic fluorophore (donor) with an o -carborane (acceptor) [ 4 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. The strong electron-withdrawing ability of the carbon atoms in the o -carborane cage, which is derived from the high polarizability of the σ-aromaticity [ 37 , 38 , 39 , 40 , 41 ], allows this moiety to act as an electron acceptor during external excitation and relaxation processes.…”

Section: Introductionmentioning

confidence: 99%

Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9H-carbazole-Based ortho-Carboranyl Luminophores

Lee

Mun

et al. 2021

Molecules

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The photophysical properties of closo-ortho-carboranyl-based donor–acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of 1F and 4T were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π–π* transition of the 9-phenyl-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λem = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S1) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for 1F < ‒H for 2P < ‒CH3 for 3M < ‒C(CH3)3 for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.

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Synthetic Emission Tuning of Carborane-Containing Poly(dihexylfluorene)s

Cited by 28 publications

References 55 publications

Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Recent Progress in the Development of Solid‐State Luminescent o‐Carboranes with Stimuli Responsivity

Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9H-carbazole-Based ortho-Carboranyl Luminophores

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