4,7-Diarylbenzo[<i>c</i>][1,2,5]thiadiazoles as fluorophores and visible light organophotocatalysts

Taylor, Dominic; Malcomson, Thomas; Zhakeyev, Adilet; Cheng, Shengxian; Rosair, Georgina M.; Marqués-Hueso, José; Xu, Zhengtao; Paterson, Martin J.; Dalgarno, Scott J.; Vilela, Filipe

doi:10.1039/d2qo01316a

Cited by 10 publications

(16 citation statements)

References 85 publications

(145 reference statements)

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“…Recently, we have reported on the effect that changing the aryl group has on the photophysical and photoredox properties of a 4,7-diarylBTZ D-A photocatalyst system. 19 These photocatalysts were broadly assembled through the use of Suzuki-Miyaura cross-coupling, with the variation in structure achieved by varying the combination of coupling partners. A more direct approach towards aryl group modication has been realised by Zhang and coworkers, who have reported both the palladium catalysed regioselective C-H acyloxylation and halogenation of 4-aryl and 4,7-diaryl substituted BTZs using hypervalent iodine reagents (Fig.…”

Section: Introductionmentioning

confidence: 68%

“…This strategy was not extended to pH-BTZ-oPh as we have previously reported the synthesis of the symmetric molecule pH-BTZ-oPh 2 directly via a single Suzuki-Miyaura cross- coupling reaction from 4,7-dibromoBTZ. 19 However, pH-BTZ-oPh 2 was also characterised in parallel with the uorophores discussed in this report as an analogue of Th-BTZ-oPh 2 .…”

Section: Fluorophore Synthesismentioning

confidence: 81%

“…Our previous studies conducted into BTZ compounds as fluorophores focused on the changes in light absorption and emission that could be made by derivatisation of pH-BTZ , which exhibited a λ abs at 380 nm and a λ em at 482 nm in chloroform. 19 The most significant changes were observed upon substitution of the phenyl rings with heterocycles, leading to significant hypsochromic ( e.g . 4-pyridyl groups) or bathochromic shifts ( e.g .…”

Section: Resultsmentioning

confidence: 99%

“…4,7-Dibromobenzo[ c ][1,2,5]thiadiazole, 31 palladium tetrakis(triphenylphosphine) (0) (Pd(PPh 3 ) 4 ), 32 4,7-diphenylbenzo[ c ][1,2,5]thiadiazole ( pH-BTZ ), 4-([1,1′-biphenyl]-2 yl)-7-phenylbenzo[ c ][1,2,5]thiadiazole ( oPh-BTZ ) and 4,7-di(thiophen-2-yl)benzo[ c ][1,2,5]thiadiazole ( Th-BTZ ) were all synthesised according to literature procedures (see ESI† for details). 19 All commercially available reagents were used as received and purchased from Sigma-Aldrich, Fluorochem, Apollo Scientific or Fischer Scientific. DCM was dried over 4 Å activated molecular sieves before using in borylation reactions.…”

Section: Methodsmentioning

confidence: 99%

“…This can be contrasted with the reported crystal structure of Th-BTZ previously reported by McCulloch and coworkers, in which both thiophene rings are coplanar with the BTZ group. 19 All commercially available reagents were used as received and purchased from Sigma-Aldrich, Fluorochem, Apollo Scientic or Fischer Scientic. DCM was dried over 4 Å activated molecular sieves before using in borylation reactions.…”

Section: Single Crystal X-ray Structuresmentioning

confidence: 99%

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Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores

et al. 2023

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Section: Introductionmentioning

confidence: 68%

Section: Fluorophore Synthesismentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Single Crystal X-ray Structuresmentioning

confidence: 99%

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Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores

et al. 2023

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Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long‐Lived Excited State

Hunt

Wijesinghe

Curiac

et al. 2022

Advanced Energy Materials

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Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long‐lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6‐dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady‐state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. The long‐lived excited state photosensitizer is well‐suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water‐soluble photosensitizer.

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Helicene Appended Benzothiadiazoles as Chiral Emitters

Martin,

Aharon,

Mastropasqua Talamo

et al. 2024

Chemistry A European J

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A homologous series of 4,7‐bis(aryl) substituted benzothiadiazole (BTD) compounds, containing the helicenic derivatives bis([4]helicene), bis([5]helicene) and bis([6]helicene), have been prepared upon a double Suzuki coupling between 3,6‐bis(pinacolyl‐borane)‐BTD and the corresponding bromo‐aryl precursors. The single crystal X‐ray structure of the bis([4]helicene) compound shows the existence of both helicities (M) and (P) on the same molecule. All the compounds of the series are highly emissive in solution, with quantum yields of the emission ranging from 50 to 91%. The enantiopure compounds (M,M) and (P,P) for the BTD‐bis([6]helicene) have been prepared from the corresponding enantiopure 2‐bromo‐[6]helicene precursors. Their chiroptical properties have been investigated in correlation with density functional theory (DFT) calculations, which allowed to confidently assign the absolute configuration of the helicene arms and to characterize the different electronic transitions, including the low energy charge transfer excitation from helicenes to BTD. The enantiomerically pure fluorophores (M,M)‐ and (P,P)‐BTD‐bis([6]helicene), which exist in solution as two main conformers, according to the DFT calculations, show CPL activity in solution, with glum factors of ≈ 1.7×10–3 at lem = 525 nm, and also in the solid state, with glum factors of ≈ 1.2×10–3 in spite of the strong decrease of the quantum efficiency.

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4,7-Diarylbenzo[c][1,2,5]thiadiazoles as fluorophores and visible light organophotocatalysts

Abstract: Electron donor-acceptor (D-A) systems based on the benzo[c][1,2,5]thiadiazole (BTZ) motif have been extensively researched for use in photovoltaics or as fluorescent sensors. However, their use as potential visible-light organophotocatalysts has...

Cited by 10 publications

References 85 publications

Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores

Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores

Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long‐Lived Excited State

Helicene Appended Benzothiadiazoles as Chiral Emitters

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