Order–Disorder, Symmetry Breaking, and Crystallographic Phase Transition in a Series of Bis(trans-thiocyanate)iron(II) Spin Crossover Complexes Based on Tetradentate Ligands Containing 1,2,3-Triazoles

[Image: see text] We report herein a series of neutral trans-thiocyanate mononuclear spin crossover (SCO) complexes, [Fe(II)L(NCS)(2)] (1–4), based on tetradentate ligands L obtained by reaction of N-substituted 1,2,3-triazolecarbaldehyde with 1,3-propanediamine or 2,2-dimethyl-1,3-diaminopropane [L = N(1),N(3)-bis((1,5-dimethyl-1H-1,2,3-triazol-4-yl)methylene)propane-1,3-diamine/-2,2-dimethylpropane-1,3-diamine, 1/2 and N(1),N(3)-bis((1-ethyl/1-propyl-1H-1,2,3-triazol-4-yl)methylene)-2,2-dimethylpropane-1,3-diamine, 3/4]. The thermal-induced SCO behavior is characterized by abrupt transitions with an average critical temperature (ΔT(1/2))/hysteresis loop width (ΔT(hyst)) in the range 190–252/5–14 K, while the photo-generated metastable high-spin (HS) phases are characterized by T(LIESST) temperatures in the range 44–59 K. Single crystal analysis shows that except 1, all compounds experience reversible symmetry breaking coupled with the thermal SCO. Furthermore, 4 experiences an additional phase transition at ca. 290 K responsible for the coexistence of two HS phases quenched at 10 K through LIESST and TIESST effects. The molecules form hexagonally packed arrays sustained by numerous weak CH···S and C···C/S···C/N···C bonds involving polar coordination cores, while non-polar pendant aliphatic substituents are segregated inside, occupying hexagonal channels. Energy framework analysis of complexes with one step SCO transition (1, 2, and 4) shows a correlation between the cooperativity and the amplitude of changes in the molecule–molecule interactions in the lattice at the SCO transition.