B(C6F5)3: A Lewis Acid that Brings the Light to the Solid State

Hansmann, Max M.; López‐Andarias, Javier; Rettenmeier, Eva; Egler‐Lucas, Carolina; Röminger, Frank; Hashmi, A. Stephen K.; Romero‐Nieto, Carlos

doi:10.1002/anie.201508461

Cited by 57 publications

(45 citation statements)

References 26 publications

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“…In this way, we demonstrated the ability to precisely control the excited‐state energy, by changing the strength or amount of the Lewis acid additive and by synthetically controlling the binding site of the chromophore. Around the same time, it was shown that coordination of B(C 6 F 5 ) 3 to non‐emissive aldehydes could engender intense color‐tunable luminescence, further highlighting the ability of Lewis acid‐base coordination chemistry to influence photophysical attributes …”

Section: Introductionmentioning

confidence: 88%

Lewis Acid Modulation of meso‐Pyridyl BODIPY Chromophores

Choung

Teets

2018

ChemPhotoChem

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Two pyridyl‐substituted boron dipyrromethene (BODIPY) compounds are shown to interact with the strong Lewis acid B(C6F5)3. The borane adducts are characterized by multinuclear NMR and in one case by X‐ray crystallography. The titration of pyridyl‐substituted BODIPYs with B(C6F5)3 results in a bathochromic shift of the UV/Vis absorption and emission spectra, with the magnitude of the shift depending on the distance of the bound borane from the BODIPY core. In meso‐4‐pyridyl‐BODIPY, binding of B(C6F5)3 induces a small circa 230 cm−1 red shift in the UV/Vis absorption maximum, with a much larger 1950 cm−1 shift in the photoluminescence maximum. In meso‐4‐pyridylphenyl‐BODIPY, where the pyridine Lewis base is separated from the BODIPY core by a phenyl spacer, smaller shifts of circa 120 cm−1 in UV/Vis absorption and 330 cm−1 in photoluminescence are observed. This work shows that these organic chromophores can interact with Lewis acids as a means of systematically perturbing the electronic structure and excited‐state properties.

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Section: Introductionmentioning

confidence: 88%

Lewis Acid Modulation of meso‐Pyridyl BODIPY Chromophores

Choung

Teets

2018

ChemPhotoChem

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“…[8,9] The pyridyl nitrogen atom of PyBTM acts as as timulus-responsive site. [21][22][23] The coordination and dissociation of B(C 6 F 5 ) 3 to and from the nitrogen atom of PyBTM was expected to reversibly change the emission colour. [14,30] In this study,w eh ave tackled two challenges that had not previously been resolved.…”

Section: Introductionmentioning

confidence: 99%

“…The first concerns reversible control of the emission colouro ft he radical by usingB (C 6 F 5 ) 3 as an externalc hemical stimulus.B (C 6 F 5 ) 3 is aL ewis acid capable of reversibly binding aL ewis base, such as the lone pair of an itrogen atom, through the vacant 2p Z orbital [18][19][20] and has been used as an additive to modulate the optical properties of molecularm aterials. [21][22][23] The coordination and dissociation of B(C 6 F 5 ) 3 to and from the nitrogen atom of PyBTM was expected to reversibly change the emission colour. The second challenge is elucidating how the chemical modificationa ffectst he electronic structure (electron density distribution and energy levels of molecular orbitals)i nm odulating the properties of radicals.…”

Section: Introductionmentioning

confidence: 99%

Modulated Luminescence of a Stable Open‐Shell Triarylmethyl Radical: Effects of Chemical Modification on Its Electronic Structure and Physical Properties

Kusamoto

Kimura

Ogino

et al. 2016

Chemistry A European J

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The open-shell luminescent (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl (PyBTM) radical contains a nitrogen atom that behaves as a stimulus-responsive site. Chemical modification at this nitrogen atom, such as coordination of B(C F ) or methylation, shifts the emission maximum to the low-energy region and increases the reduction potential. The emission colour may be regulated by the reversible Lewis acid-base reaction between B(C F ) and PyBTM. Comparison of the optical and electrochemical properties of the radicals with the electronic structures calculated by density functional theory has indicated that the chemical modification decreased the energy level of the β-singly occupied molecular orbital, a key orbital in determining the optical and electrochemical properties of such systems.

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“…Only a few successful demonstrations of solid-state emission induced by non-covalent interactions have been reported. These include a coordination bond between the p-orbital of borane compounds and the oxygen atom of aldehydes 18 , acid-base interactions 19 , isolation of uorescent dyes by ionic lattices 20 and an anion-π + interaction 21 . The introduction of electron-donating and electronwithdrawing groups to π-conjugated molecular systems with rotatable covalent bonds is a strategy for AIEE dye synthesis.…”

Section: Introductionmentioning

confidence: 99%

Viscosity-sensitive emission of anionic hydrogen-bonded urea-derivative–acetate-ion complexes and their aggregation-induced emission enhancement

Takahashi¹,

Ito²,

Ninagawa³

et al. 2020

Preprint

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Anions often quench fluorescence (FL). However, strong ionic hydrogen bonding between fluorescent dyes and anion molecules has the potential to control the electronic state of FL dyes, creating new functions via non-covalent interactions. Here, we propose a novel approach, utilising ionic hydrogen bonding between urea groups and anions, to control the electronic states of fluorophores and develop an aggregation-induced emission enhancement (AIEE) system. The AIEE ionic hydrogen-bonded complex (IHBC) formed between 1,8-diphenylnaphthalene (p-2urea), with aryl urea groups at the para-positions on the peri-phenyl rings, and acetate ions exhibits a remarkably high sensitivity to fluid viscosity compared with most conventional viscosity-sensitive dyes, and the FL quantum yield (QY) in ion-pair assemblies of the IHBC and tetrabutylammonium cations is more than five times higher than that of the IHBC in solution. Our versatile and simple approach for the design of AIEE dye facilitates the future development of viscosity probes and solid-state emitting materials.

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B(C₆F₅)₃: A Lewis Acid that Brings the Light to the Solid State

Cited by 57 publications

References 26 publications

Lewis Acid Modulation of meso‐Pyridyl BODIPY Chromophores

Lewis Acid Modulation of meso‐Pyridyl BODIPY Chromophores

Modulated Luminescence of a Stable Open‐Shell Triarylmethyl Radical: Effects of Chemical Modification on Its Electronic Structure and Physical Properties

Viscosity-sensitive emission of anionic hydrogen-bonded urea-derivative–acetate-ion complexes and their aggregation-induced emission enhancement

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