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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Burton, Spencer T ; Lee, Gyunhee ; Moore, Curtis E ; Sevov, Christo S ; Turro, Claudia ;
Abstract: The Co(III) complexes, cis-[Co(ppy)2(L)]PF6, where ppy = 2-phenylpyridine and L = bpy (2,2′-bipyridine; 1), phen (1,10-phenanthroline; 2), and DAP (1,12-diazaperylene; 3), are reported and their photophysical properties were investigated to evaluate their potential as sensitizers for applications that include solar energy conversion schemes and photoredox catalysis. Calculations show that cyclometallation in the cis-[Co(ppy)2(L)]PF6 series affords strong Co(dπ)/ppy(π) orbital interactions that result in a Co/ppy(π*) highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) localized on the diimine ligand, L(π*). Complexes 1−3 exhibit relatively invariant oxidation potentials, whereas the reduction event is dependent on the identity of the diimine ligand, L, consistent with the theoretical predictions. For 3 a broad Co/ppy(π*) → L(π*) metal/ligand-to-ligand charge transfer (ML-LCT) absorption band is observed in CH3CN with a maxima at 507 nm, extending beyond 600 nm. Upon excitation of the 1 ML-LCT transition, transient absorption features consistent with the population of a 3ML-LCT excited state with lifetimes, τ, of 3.0 ps, 4.6 and 42 ps for 1, 2 and 3 in CH3CN respectively are observed. Upon irradiation with 505 nm, 3 is able to reduce methyl viologen (MV2+), an electron acceptor commonly in photocatalytic schemes. To our knowledge, 3 represents the first heteroleptic molecular Co(III) complex that combines cyclometallation with a diimine ligand with lowest-lying metal-to-ligand charge transfer excited states able to undergo photoinduced charge transfer with low-energy green light. As such, the structural design of 3 represents an important step toward d6 photosensitizers based on earth abundant metals.
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CAS No. : | 119-65-3 |
Formula : | C9H7N |
M.W : | 129.16 |
SMILES Code : | C12=C(C=NC=C2)C=CC=C1 |
MDL No. : | MFCD00006898 |
InChI Key : | AWJUIBRHMBBTKR-UHFFFAOYSA-N |
Pubchem ID : | 8405 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H311-H302-H315-H319-H412 |
Precautionary Statements: | P501-P273-P270-P264-P280-P337+P313-P305+P351+P338-P361+P364-P332+P313-P301+P312+P330-P302+P352+P312-P405 |
Class: | 6.1 |
UN#: | 2811 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
92% | With [bis(acetoxy)iodo]benzene; chloroformic acid ethyl ester In 1,2-dichloro-ethane at 50℃; for 3 h; | General procedure: To an 8 mL dram vial was added iodobenzene diacetate (0.6 mmol, 1.5 equiv), and heteroarene(0.4 mmol, 1 eq.), anhydrous dichloroethane (1 mL), then chloride source (5 equiv). The solutionwas allowed to stir (1000 rpm) at 50 °C for the indicated amount of time. After which the solutionwas washed with saturated sodium bicarbonate, followed by saturated sodium thiosulfate andconcentrated. The crude mixture was then purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Isoquinoline ( 13a) (1.83 ml, 15.50 mmol) was added slowly to concentrated H2SO4 ( 17 ml) at 0C under stirring. The mixture was cooled at -25C and sodium borohydride (6.34 g, 35.65 mmol) was added at a rate such that the reaction temperature was maintained between -25C to -20C. The resulting reaction was continued for 1 hour at the said temperature and then allowed to reach at room temperature. The reaction mixture was poured into crushed ice and the pH was adjusted to 7.0 using concentrated aqueous N¾. The resulting slurry was stirred for 1 hour at 0C after which it was filtered and washed with ice-cold water. The crude product so obtained was air dried and purified by column chromatography to afford (2.5 g, 56%) 5,8-dibromoisoquinoline (13b). MS (EI) rn/z: 286 (M+l). ? NMR (400 MHz, DMSO-d6): 8 9.48 (s, 1H), 8.78 (d, J = 6 Hz, 1H), 8.06 (d, J = 8 Hz, 1H), 7.98 (dd, J = 6 Hz, J = 8 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With palladium 10% on activated carbon; hydrogen; In ethanol; at 20℃; under 760.051 Torr; | 1-chloro-4-fluoroisoquinoline (9a) obtained by the method of Example 3(55 mg) in ethanol (2 mL)10percent Pd charcoal (26 mg; containing 54percent moisture) was added,Under 1 atm hydrogen atmosphere at room temperature until reductive cracking is complete (5 to 15 h)Followed by stirring. The catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure.The residue was dissolved in ethyl acetate-water to remove the aqueous layer, the organic layer was washed with 20percent brine, and dried over anhydrous magnesium sulfate.The solvent was distilled off under reduced pressure to give 4-fluoroisoquinoline (1)And isoquinoline (33 mg) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With trichloroisocyanuric acid; sulfuric acid; at 0 - 10℃; for 24h; | To mechanically stirred concd H 2 SO 4 (100 mL), isoquinoline (1; 12.9 g,0.1 mol, 1.0 equiv) was slowly added at 0 C. During intensive stirringTCCA (12.8 g, 55 mmol, 1.65 equiv) was then added in 4 portionswhile the reaction temperature was kept at 10 C. The mixture wasthen stirred at 10 C and followed by GC-MS. After 24 h the reactionmixture was poured onto crushed ice (ca. 200 g) and the precipitatewas filtered. The pH of the filtrate was adjusted to 2 with concd aqNH 3 solution with extensive cooling. The slurry was then filtered. Thefiltrate was extracted with toluene (6 × 75 mL) to remove the sideproduct, 5,8-dichloroisoquinoline (16). The aqueous phase was fur-ther basified with concd aq NH 3 solution until pH 6 was reached. Atthis point the precipitate was filtered, washed with H 2 O, and dried inair. Finally, the filtrate was recrystallized from methylcyclohexane toafford 15.Yield: 7.60 g (45%); mp 70-72 C.IR (ATR): 1580, 1489, 1371, 1267, 1204, 1140, 1065, 984, 822, 750,687, 628, 536 cm -1 .1 H NMR (400 MHz, CDCl 3 ): δ = 9.27 (s, 1 H), 8.64 (d, J = 6.0 Hz, 1 H),8.02 (d, J = 6.0 Hz, 1 H), 7.90 (d, J = 8.2 Hz, 1 H), 7.77 (d, J = 7.5 Hz, 1 H),7.53 (t, J = 7.8 Hz, 1 H).13 C NMR (100 MHz, CDCl 3 ): δ = 152.4, 143.9, 133.7, 131.0, 130.3,129.4, 127.3, 126.7, 116.9. |
Tags: 119-65-3 synthesis path| 119-65-3 SDS| 119-65-3 COA| 119-65-3 purity| 119-65-3 application| 119-65-3 NMR| 119-65-3 COA| 119-65-3 structure
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