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Chemical Structure| 6813-38-3 Chemical Structure| 6813-38-3
Chemical Structure| 6813-38-3

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Goodwin, Matthew J ; Deetz, Alexander M ; Griffin, Paul J ; Meyer, Gerald J ;

Abstract: The preassociation of reactants in a photoinitiated redox reaction through the use of noncovalent interactions can have a significant impact on excited state reactivity. As these noncovalent interactions render some stabilization to the associated species, they impact the kinetics and thermodynamics of photoinitiated electron transfer. Reported herein is a novel iridium(III) photocatalyst, equipped with an anion-sensitive, amide-substituted bipyridine ligand, and its reactivity with the halides (X = I, Brsup>−, Clsup>−) in acetonitrile and dichloromethane. A noteworthy periodic trend was observed, where the size and electron affinity dramatically altered the observed photoredox behavior. The binding affinity for the halides increased with decreasing ionic radius (Keq ~103 to >106 ) in a polar medium but association was stoichiometric for each halide in a nonpolar medium. Evidence for the static quenching of and is presented while dynamic quenching was observed with all halides. These results highlight how the photophysics of halide adducts and the thermodynamics of intra-ionic photo-oxidation are impacted as a consequence of preassociation of a quencher through hydrogen bonding.

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Product Details of [2,2'-Bipyridine]-4,4'-dicarboxylic acid

CAS No. :6813-38-3
Formula : C12H8N2O4
M.W : 244.20
SMILES Code : O=C(C1=CC(C2=NC=CC(C(O)=O)=C2)=NC=C1)O
MDL No. :MFCD00015430
InChI Key :FXPLCAKVOYHAJA-UHFFFAOYSA-N
Pubchem ID :688094

Safety of [2,2'-Bipyridine]-4,4'-dicarboxylic acid

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [2,2'-Bipyridine]-4,4'-dicarboxylic acid

* 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.

  • Downstream synthetic route of [ 6813-38-3 ]

[ 6813-38-3 ] Synthesis Path-Downstream   1~5

  • 3
  • [ 52462-29-0 ]
  • [ 6813-38-3 ]
  • [ 1189458-67-0 ]
  • [ 1147550-11-5 ]
  • [RuII(4,4'-dicarboxy-2,2'-bipyridyl)(4,4'-dithiocyanate-2,2'-bipyridyl)dithiocyanate] [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% A mixture of [Ru(p-cymene)Cl2]2 (102.7 mg, 0.16 mmol) and H2-dcbpy (81.3 mg, 0.33 mmol) were heated under N2 in dry DMF (20 ml) at 60 C overnight. 4,4'-F2-bpy (63.7 mg, 0.33 mmol) was added and the temperature increased to 140 C for 2 h. Excess NH4NCS (1.0073 g, 13.23 mol, 40 times excess) was then added and heating continued at 140 C for 3 h. After allowing to cool, the solvent was then removed using reduced pressure and the resulting black solid stirred in water overnight to remove any unreacted NH4NCS. Upon filtering the crude product was formed as a darkred/brown solid. Purification was achieved by dissolving the crude product in NaOH solution (0.1 M, in methanol) and performing Sephadex column chromatography using methanol as the eluent. This produced the pure product 1 (69.8 mg, 0.10 mmol, 60% yield)as a dark red solid. 1H NMR (600 MHz, CD3OD) delta (ppm): 9.54 (d,J = 5.7 Hz, 1H), 8.93 (s, 1H), 8.85 (d, J = 6.7 Hz, 1H), 8.78 (s, 1H),8.15 (dd, J = 5.6 Hz, 1.6 Hz, 1H), 7.76 (d, J = 6.0 Hz), 7.53 (dd,J = 5.9 Hz, 1.6 Hz, 1H), 7.52 (s, 1H), 7.40 (s, 1H), 7.01 (dd,J = 6.60 Hz, 2.47 Hz, 1H), 6.85 (d, J = 6.9 Hz, 1H), 6.32 (dd,J = 6.7 Hz, 2.6 Hz, 1H). ESI-MS: m/z 730 [M-H]-. Anal. Calc.: C,44.10; H, 2.18; N, 12.91. Found: C, 44.08; H, 2.13; N, 12.80%.
  • 4
  • ruthenium(III) chloride trihydrate [ No CAS ]
  • [ 6813-38-3 ]
  • ammonium thiocyanate [ No CAS ]
  • [ 142646-58-0 ]
  • [ 502693-09-6 ]
YieldReaction ConditionsOperation in experiment
61% 0.851 g of ruthenium (III) chloride hydrate and 40 ml ofN-methylpyrrolidone were added to the first reactor and (4,4'-dinonyl-2,2'bipyridine)was added thereto while stirring and the mixture was stirred for 0.5 hour. In the second reactor, ligand 2(2,2'-bipyridine-4,4'-dicarboxylicacid) and 60 ml of N-methylpyrrolidone were placed and maintained at 140 to 150 C. The mixed solution of the first reactor was added to the secondreactor, stirring was continued for 1.5 hours while maintaining the temperatureat 140 to 150 C, and ammonium thiocyanate 5.16 g was added and stirred for 1hour and then the reactor was cooled. The reaction mixture was poured into distilled water toprecipitate a solid. The solid was dissolved in 40 ml of methanol and NaOH wereused to maintain the pH of 10 to 11. After purification by column usingSephadex resin, the solution was adjusted to pH 4.8 with nitric acid to give togive the desired compound as a solid.
  • 5
  • [ 52462-29-0 ]
  • [ 6813-38-3 ]
  • ammonium thiocyanate [ No CAS ]
  • [ 142646-58-0 ]
  • [ 502693-09-6 ]
YieldReaction ConditionsOperation in experiment
28% General procedure: 0.851 g of ruthenium (III) chloride hydrate and 40 ml of N-methylpyrrolidone were added to the first reactor(4,4'-dinonyl-2,2'bipyridine) was added thereto while stirring and the mixture was stirred for 0.5 hour. In the second reactor, ligand 2(2,2'-bipyridine-4,4'-dicarboxylic acid) and 60 ml of N-methylpyrrolidone were placed and maintained at 140 to 150 C. The mixed solution of the first reactor was added to the second reactor,Stirring was continued for 1.5 hours while maintaining the temperature at 140 to 150 C, and ammonium thiocyanate5.16 g was added and stirred for 1 hour and then the reactor was cooled. The reaction mixture was poured into distilled water to precipitate a solid. The solid was dissolved in methanol40 ml and NaOH were used to maintain the pH of 10 to 11, After purification by column using Sephadex resin,the solution was adjusted to pH 4.8 with nitric acid to give a solid to give the desired compound. Instead of ruthenium (III) chloride hydrate, [RuCl2 (p-cymene)] 2 Except that the complex compound was used, a heteroleptic ruthenium complex dye was synthesized in the same manner.
 

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