First W-band 94 GHz EPR spectra of randomly oriented triplet, quintet, and septet nitrenes formed during the photolysis of 1,3,5-triazido-2,4,6-tribromobenzene in cryogenic matrices are reported. In comparison with conventional X-band 9 GHz electron paramagnetic resonance (EPR) spectroscopy, W-band EPR spectroscopy allows the detection and complete spectroscopic characterization of all paramagnetic species formed at different stages of the photolysis of aromatic polyazides. This type of spectroscopy is of paramount importance for experimental determination of the sign of the zero-field splitting (ZFS) parameters of high-spin molecules with large spin-orbit contribution to the ZFS, caused by the effect of heavy atoms. The study shows that triplet 1,3-diazido-2,4,6-tribromo-5-nitrenobenzene (T1) has DT = 1.369 cm(-1), ET = 0.093 cm(-1), and g = 2.0033, quintet 1-azido-2,4,6-tribromo-3,5-dinitrenobenzene (Q1) shows DQ = - 0.306 cm(-1), EQ = 0.0137 cm(-1), and g = 2.0070, and septet 2,4,6-tribromo-1,3,5-trinitrenobenzene (S1) has DS = - 0.203 cm(-1), ES = 0, and g = 2.0073. The experimental ZFS parameters agree well with the results of density functional theory calculations at the PBE/Ahlrichs-DZ level of theory, showing that such calculations adequately describe the magnetic properties of bromine-containing high-spin nitrenes. Both experimental and theoretical data indicate that, in contrast to all known to date quintet dinitrenes, dinitrene Q1 has the negative sign of magnetic anisotropy due to the "heavy atom effect." This dinitrene along with septet trinitrene S1 possess the largest negative value of D among all known quintet and septet organic polyradicals.