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Qing Yun Li ; Leigh Anna Hunt ; Kalpani Hirunika Wijesinghe ; Christine Curiac ; Ashley Williams ; Amala Dass , et al.
Abstract: 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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Purchased from AmBeed: 54512-79-7 ; 5798-75-4 ; 328-70-1 ; 586-76-5 ; 22385-77-9 ; 3109-63-5 ; 23783-42-8 ; 3375-31-3 ; 1122-58-3 ; 479094-62-7 ; 75-98-9 ; 51364-51-3 ; 538-75-0 ; 584-08-7 ; 1122-91-4 ; 123-30-8 ; 108-88-3 ; 109-77-3 ; 64-19-7 ; 603-35-0
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| CAS No. : | 54512-79-7 |
| Formula : | C8H2N4S |
| M.W : | 186.19 |
| SMILES Code : | N#CC1=CC2=NSN=C2C=C1C#N |
| English Name : | Benzo[c][1,2,5]thiadiazole-5,6-dicarbonitrile |
| MDL No. : | MFCD27964187 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 80.4% | With thionyl chloride; triethylamine In dichloromethane at 50℃; for 5h; | |
| 80.4% | With thionyl chloride; triethylamine In dichloromethane at 50℃; for 5h; Cooling with ice; | 1.1 (1) Synthesis of Compound 2 Compound 1 (5.0 g, 31.6 mmol), dichloromethane (30 mL), and triethylamine (30 mL) were added to a round-bottom flask. In an ice-water bath, SOCl2 (25 mL, 344 mmol) and CH2Cl2 (25 mL) were slowly added dropwise to form a mixed solution. After the mixed solution was stirred at 50 ° C for 5 hours, a saturated Na2CO3 aqueous solution was added and stirred for 15 minutes. The filtrate was filtered and extracted with dichloromethane.After removing the solvent, the mixture was purified by column (eluent was petroleum ether: dichloromethane = 1:4, v/v) to obtain a light yellow solid (4.73 g, yieldwas 80.4%), which was compound 2. |
| 68% | With thionyl chloride for 5h; Heating; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 70% | With iron In acetic acid for 0.5h; Reflux; | |
| 53% | With sodium tetrahydroborate In ethanol at 20℃; for 12h; | |
| Stage #1: benzo[c]-[1,2,5]thiadiazole-5,6-dicarbonitrile With cobalt(II) chloride hexahydrate In tetrahydrofuran; ethanol for 0.25h; Stage #2: With sodium tetrahydroborate In tetrahydrofuran; ethanol for 2h; Reflux; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 67% | With copper(l) iodide In nitrobenzene; N,N-dimethyl-formamide for 9h; Reflux; | |
| 66% | Stage #1: copper(l) cyanide; 5,6-dibromobenzo[c][1,2,5]thiadiazole In N,N-dimethyl-formamide for 3h; Heating; Stage #2: With hydrogenchloride; iron(III) chloride In water at 70℃; for 0.5h; Further stages.; | |
| In N,N-dimethyl-formamide |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 60% 2: 10% | Stage #1: 5,6-dibromobenzo[c][1,2,5]thiadiazole With copper(l) iodide; copper(l) cyanide In nitrobenzene; N,N-dimethyl-formamide for 6h; Reflux; Stage #2: With hydrogenchloride; iron(III) chloride In water; nitrobenzene; N,N-dimethyl-formamide at 70℃; for 1h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 99% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; | |
| With di-tert-butyl(methyl)phosphonium tetrafluoroborate; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; | 1 Arylation on benzo[c][1,2,5]thiadiazole-5,6-dicarbonitrile (DCBT) by aryl bromide To an oven-dried 5 mL collared tube (CEM Corp., Prod 89079-404) containing a stirring bar, Pd(OAc)2 (2.8 mg, 0.013 mmol), PtBu2Me.HBF4 (6.2 mg, 0.025 mmol), pivalic acid (12.3 mg, 0.125 mmol), benzo[c][1,2,5]thiadiazole-5,6-dicarbonitrile (DCBT, 21.5 mg, 0.125 mmol), potassium carbonate (54 mg, 0.38 mmol), and arylbromide (0.275 mmol) were sequentially added under a flow of N2. Anhydrous toluene (0.4 mL) was added and a septum-cap was crimped on the vial to form a seal. The reaction mixture was heated in a 120° C. oil bath for 3-10 h until the reaction was judged complete by examining aliquots with GC/MS or 1H NMR spectroscopy. The resulting mixture was cooled to room temperature and filtered through a layer of Celite (5 mL) using dichloromethane (DCM). The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: hexanes/DCM) affording the corresponding diarylated product. (0063) Various aryl bromides having different electronic properties (i.e. electron-rich or -poor) were used to obtain the following bis-arylated products. In addition, heteroarenes were also used and well tolerated. Furthermore, a broad range of functional groups, including aryl ester, aldehyde, and trimethylsilyl, were compatible under the reaction conditions. | |
| 90 % | With tris-(dibenzylideneacetone)dipalladium(0); di-tert-butyl(methyl)phosphonium tetrafluoroborate; potassium carbonate; Trimethylacetic acid at 110℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 99% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; for 9h; Inert atmosphere; Sealed tube; | 7-8 General Procedure for Pd(II)-catalyzed direct diarylation of DCBT, DCBTz, and DCQ To an oven-dried 5 mL collared tube (CEM Corp., Prod 89079-404) containing a stirring bar, Pd(OAc)2 (1.4 mg, 0.006 mmol), PtBu2Me.HBF4 (3.1 mg, 0.012 mmol), pivalic acid (12.3 mg, 0.125 mmol), DCBT (23.3 mg, 0.125 mmol), potassium carbonate (52 mg, 0.38 mmol), and arylbromide (0.275 mmol unless otherwise noted) were sequentially added under a flow of N2 for the arylation of DCBT derivatives. Anhydrous toluene (0.5 mL) was added and a septum-cap was crimped on the vial to form a seal. The reaction mixture was heated in a 120° C. oil bath for a certain amount of time until the reaction was judged complete by examining aliquots with GC/MS or 1H NMR spectroscopy. The resulting mixture was cooled to room temperature and filtered through a layer of Celite (5 mL) using dichloromethane (DCM). The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: hexanes/DCM or DCM/ethyl acetate), affording the corresponding diarylated products. The same procedure was used for DCBTz and DCQ derivatives using DCBTz (28.1 mg, 0.125 mmol) or DCQ (29.8 mg, 0.125 mmol) in place of DCBT and using double the catalyst and ligand loading, i.e. 0.012 mmol of Pd(OAc)2 and 0.024 mol of PtBu2Me.HBF4. |
| 99% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 89% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 86% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 76% | With di-tert-butyl(methyl)phosphonium tetrafluoroborate; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; | |
| 17 % | With tris-(dibenzylideneacetone)dipalladium(0); di-tert-butyl(methyl)phosphonium tetrafluoroborate; potassium carbonate; Trimethylacetic acid In toluene at 110℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 54 % | With di-tert-butyl(methyl)phosphonium tetrafluoroborate; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 75.8% | With hydrogenchloride; acetic acid In water at 130℃; for 32h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 75.8% | With hydrogenchloride In water at 130℃; for 32h; | 1.2 (2) Synthesis of Compound 3 Compound 2 (2.4 g, 12.9 mmol) obtained in step (1), acetic acid (30 mL), water(20 mL), and concentrated hydrochloric acid (30 mL, 37% HCl, 363 mmol) were added to a round-bottom flask to form a mixed solution. The mixed solution was stirred at 130°C for 32 h.After removing the solvent, acetone was added to dissolve the product. Filter and collect the filtrate. After removing the solvent, dry to obtain a light yellow solid (2.19 g, yield 75.8%), which is compound 3. |