m-Phenylene-linked biscarbenes, bisnitrenes and carbenonitrenes can be formed photochemically from appropriate nitrogenous precursors. Generation of such reactive intermediates under matrix-isolation conditions allows for their characterization by spectroscopic techniques such as ESR, UV /vis and IR. The latter method is also useful in characterizing secondary products derived from these reactive intermediates. Computational chemistry methods complement experimental IR data, aiding, thus, in identification of such compounds. In addition electronic structure calculations help in developing qualitative and semi-quantitative models, which can be useful in predicting ground-state multiplicities. The parent systems of m-phenylene-linked carbenes and nitrenes have high-spin ground states, but a switching to lower multiplicity can be achieved by chemical substitution. The ground state and various low-lying excited states of m-phenylenecarbenonitrenes can be reasonably approximated by simple valence-bond depictions. Finally, m-phenylenecarbenonitrenes are photoreactive in the inert matrix isomerizing to cyclopropene derivatives.