American Chemical Society
The Journal of Organic Chemistry
The reaction between 2-pyrazolyl-4-X-anilines, H(pzAnX), (X = para-OMe (L1), Me (L2), H (L3), Cl (L4), CO2Et (L5), CF3 (L6), CN (L7)) and triphenylboron in boiling toluene affords the respective, highly emissive N,N‘-boron chelate complexes, BPh2(pzAnX) (X = para-OMe (1), Me (2), H (3), Cl (4), CO2Et (5), CF3 (6), CN (7)) in high yield. The structural, electrochemical, and photophysical properties of the new boron complexes can be fine-tuned by varying the electron-withdrawing or -donating power of the para-aniline substituent (delineated by the substituent's Hammett parameter). Those complexes with electron-withdrawing para-aniline substituents such as CO2Et (5), CF3 (6), and CN (7) have more planar chelate rings, more ‘quinoidal' disortion [sic] in the aniline rings, greater chemical stability, higher oxidation potentials, and more intense (φF = 0.81 for 7 in toluene), higher-energy (blue) fluorescent emission compared to those with electron-donating substituents. Thus, for 1 the oxidation potential is 0.53 V versus Ag/AgCl (compared to 1.12 V for 7), and the emission is tuned to the yellow-green but at an expense in terms of lower quantum yields (φF = 0.07 for 1 in toluene) and increased chemical reactivity. Density functional calculations (B3LYP/6-31G*) on PM3 energy-minimized structures of the ligands and boron complexes reproduced experimentally observed data and trends and provided further insight into the nature of the electronic transitions.
Liddle, Brendan J.; Silva, Rosalice M.; Morin, Tyler James; Macedo, Felipe P.; Shukla, Ruchi; Lindeman, Sergey V.; and Gardinier, James R., "BORAZANs: Tunable Fluorophores Based on 2-(Pyrazolyl)aniline Chelates of Diphenylboron" (2007). Chemistry Faculty Research and Publications. 629.