Spectroscopic studies of azides and nitrenes derived from anthracene

9‐Azidoacridine and 9‐acridinylnitrene

“…2). The zero‐field splitting parameter | D | for the nitrene, 0.5196 cm −1 , is close to the value for 9‐anthracenylnitrene (0.47 cm −1 ) 34. The nitrene | D | values show an excellent correlation35 with the calculated spin densities on the nitrene–nitrogen (see Supporting Information, Fig.…”

A Laser Flash Photolysis and Computational Chemistry Study of 9-Anthrylnitrene

“…This was demonstrated by recording the electronic spectra ,− and EPR spectra , of triplet 1-, 2-, and 9-anthracenylnitrenes in organic matrixes at 77 K. The D parameters of these nitrenes were determined to be 0.65, 0.75, and 0.47 for 1-, 2-, and 9-anthracenylnitrenes, respectively. Compared to the D values of phenylnitrene (1.00) and 1- and 2-naphthylnitrene (0.79, 0.89−0.93), the smaller D value of anthracenylnitrenes demonstrates the increased delocalization and average separation of the two unpaired electrons. , The 9-isomer has the smallest D value of the three anthracenylnitrenes, demonstrating that the 9-position is the better conjugating position.…”

“…1-, 2-, and 9-anthracenylnitrenes have triplet ground states as do phenylnitrene and the naphthylnitrenes. This was demonstrated by recording the electronic spectra 14,[16][17][18][19] and EPR spectra 14,20 of triplet 1-, 2-, and 9-anthracenylnitrenes in organic matrixes at 77 K. The D parameters of these nitrenes were determined to be 0.65, 0.75, and 0.47 for 1-, 2-, and 9-anthracenylnitrenes, respectively. Compared to the D values of phenylnitrene (1.00) and 1-and 2-naphthylnitrene (0.79, 0.89-0.93), the smaller D value of anthracenylnitrenes demonstrates the increased delocalization and average separation of the two unpaired electrons.…”

“…However, this calculation is too large to perform with our resources. In practice, active spaces of (14,14) and (12,12) were employed, for which the first or first two highest π* and lowest π MOs were excluded, respectively. The calculated values of ∆E ST obtained in this manner are given in Table 1.…”

“…9-Azidoanthracene. , 1.135 g (5.88 mmol) of 9-aminoanthracene was added to a predried two-necked round-bottom flask and dissolved in 20 mL of anhydrous THF. The solution was cooled in an ice bath and purged with argon.…”