Four new alkyl chain appended dipyridylamino-substituted-s-triazine ligands have been incorporated into seven new, mononuclear M^II compounds of type [M^II(NCX)₂(L)₂] (where NCX = NCS⁻ or NCSe⁻, L = dipyridylamino-substituted-s-triazine-based ligand and M^II = Fe or Co). These complexes have been structurally and magnetically characterised. The magnetic consequence of varying the alkyl chain length has been investigated in terms of intermolecular interactions and crystallographic packing arrangements. For selected complexes photomagnetic LIESST (Light-Induced Excited Spin State Trapping) measurements have been performed revealing reversible photo-induced spin-state switching.