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Marisa James ; Madelyn R. Shevlin ; Thomas B. Green , et al. Inorganics,2023,11(9):353. DOI: 10.3390/inorganics11090353
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Abstract: Pyrazino-phenanthroline ligands are commonly used with transition metals as DNA intercalation agents. Herein, we report the characterization of two commonly utilized pyrazino-phenanthroline ligands, dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq) and (benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), by single-crystal X-ray diffraction. Additionally, the characterization of [Ir(ppy)2(dppn)][PF6], where Hppy = 2-phenylpyridine, by single-crystal X-ray diffraction is described. Both the dpq and dppn ligands crystallize as chloroform solvates where the chloroform molecule occupies the equivalent binding pocket of a metal in metal complexes of these ligands. These pyrazino-phenanthrolines are largely planar, with the dppn ligand displaying a slight twist. When the dppn ligand is coordinated to iridium(III), the dppn ligand on the resulting complex displays a significant degree of bending along the longitudinal direction of the ligand. This iridium (III) complex crystallizes as a CH2Cl2 and Et2O solvate and due to the volatility of these solvents these crystals are only stable for a few seconds outside of the mother liquor. The structures of the free ligands and the [Ir(ppy)2(dppn)][PF6] complex all display extensive π stacking interactions.
Keywords: pyrazino-phenanthroline ; dpq ; dppn ; intercalation ; iridium (III) complex
Purchased from AmBeed: 27318-90-7
CAS No. : | 27318-90-7 | MDL No. : | MFCD00014473 |
Formula : | C12H6N2O2 | Boiling Point : | - |
Linear Structure Formula : | (O)2(C12H6N2) | InChI Key : | KCALAFIVPCAXJI-UHFFFAOYSA-N |
M.W : | 210.19 | Pubchem ID : | 72810 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
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With ammonium acetate; L-proline; In methanol; at 60℃; for 3h; | In a 50 mL round bottom flask 1,10-phenanthroline-5,6-dione (4.7 mmol), 1H-benzimidazole-2-carbaldehyde (5 mmol) and ammonium acetate (10 mmol) were taken in presence of 15 molpercent of L-proline in methanol (20 mL). Then the reaction mixture was stirred at 60 C for 3 h. After completion of the reaction, volume of the reaction mixture was reduced, diluted with water and extracted with ethyl acetate. Organic layer was dried over anhydrous MgSO4 and then solvent was removed under reduced pressure. Crude product was washed with n-hexane and recrystallized from ethanol to obtain the pure product. Anal. Calc. for C20H12N6: C, 71.42; H, 3.59; N, 24.99. Found: C,71.33; H, 3.62; N, 25.05percent; |
Yield | Reaction Conditions | Operation in experiment |
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With potassium carbonate; In ethanol; water; for 0.666667h;Reflux; Inert atmosphere; | dadppz was synthesized according to modified method [24]. Briefly, a mixture of 1,10-phenanthroline-5,6-dione (0.252 g, 1.2 mM), 1,2,4,5-benzenetetramine tetrahydrochloride (0.341 g, 1.2 mM), and potassium carbonate (0.331 g, 2.4 mM) in ethanol (50mL) and H2O (5 mL) was refluxed under argon for 40 min. After the reaction mixture was allowed to stand at room temperature, the precipitate was filtered and washed with 10 mL ethanol. The filtrate was evaporated under reduced pressure to 5mL. Upon cooling, a red precipitate was obtained by dropwise addition of water. ES-MS (CH3CN, m/z): 313.3 [M + 1]+. |