Two bis(unsymmetrical diimine) complexes of (L(NO(2))(ϕ1))(L(NO(2))(ϕ2))M(II)Cl(2) family with M = Fe and Mn, are reported (L(NO(2))(ϕ) = (E)-3-nitro-N-(pyridine-2-ylmethylene)aniline; ϕ = dihedral angle between the diimine unit including pyridine ring and the phenyl ring planes). Pure tcc-(L(NO2)(33.6))(L(NO2)(79.3))Fe(II)Cl(2)·0.5H(2)O (1) and tcc-(L(NO2)(32.0))(L(NO2)(79.4))Mn(II)Cl(2)·0.5H(2)O (2) isomers have been successfully isolated in high yields and characterized by elemental analyses, variable temperature magnetic susceptibility measurements, IR, mass, UV-vis and Mössbauer spectra including the single-crystal X-ray structure determinations that identified strong intermolecular non-bonding interactions in lattice (tcc refers to trans-cis-cis positions with respect to pyridine N-imine N-Cl donors). Geometries optimizations of all possible tcc, ttt, ctc, ccc and cct isomers of iron at the B3LYP/DFT level in gas-phase have shown that the tcc-isomer incorporating two non-equivalent ligands as in (L(NO(2))(42))(L(NO(2))(61))Fe(II)Cl(2), 1 (g), is stabilized by 6-20 kJ mol(-1) compared to other isomers where two ligands are equivalent. The frozen methanol glasses of 1 and 2 are luminescent at 77 K (1: λ(ext) = 370, λ(em) = 521 nm, χ(2) = 1.3, τ(avg) = 0.57 ns; 2: λ(ext) = 368, λ(em) = 524 nm, χ(2) = 1.1, τ(avg) = 0.90 ns). The DFT calculations have identified four closely spaced localized π(*) orbitals comprising of two non-equivalent ligands as UPMOs. The features contrast the tcc-isomer of (L(ϕ))(2)Fe(II)Cl(2) (3), congener of 1 without -NO(2) substitution and non-emissive (bpy)(2)Fe(II)Cl(2) (4) where two ligands are equivalent. TD-DFT calculations have assigned intra-ligand (IL) and ligand to ligand charge transfer (LLCT) dominated excited states as the origin of luminescence of 1 and 2.