Ising-Like Model Hasn't Yet Said Its Last Word: Exact and Mean-Field Investigations of 2, 3 and 4-Body Interactions in 1D Ising Chain of Binuclear Spin-Crossover Solids.

We investigate the static properties of a new class of 1D Ising-like Hamiltonian for binuclear spin-crossover materials accounting for two-, three-, and four-body short-range interactions between binuclear units of spins ( s 1 A , s 1 B ) ${(s_1^A, s_1^B )}$ and ( s 2 A , s 2 B ) ${(s_2^A, s_2^B )}$ . The following 2-, 3-, and 4-body J 1 ( s 1 A + s 1 B ) ( s 2 A + s 2 B ) ${J_1 (s_1^A + s_1^B )(s_2^A + s_2^B )}$ , K 1 s 1 A s 1 B ( s 2 A + s 2 B ) ${K_1 s_1^A s_1^B (s_2^A + s_2^B )}$ , and K 2 ( s 1 A s 1 B ) ( s 2 A s 2 B ) ${K_2 (s_1^A s_1^B )(s_2^A s_2^B )}$ terms are considered, in addition to intra-binuclear interactions, such as effective ligand-field energy and exchange-like coupling. An exact treatment is carried out within the frame of the transfer matrix method, leading to a 4×4 matrix from which, we obtained the thermal evolution of the thermodynamic quantities. Several situations of model parameter values were tested, among which that of competing intra- and inter-molecular interactions, leading to the occurrence of (i) one-step spin transition, (ii) two-, three-, and four-step transitions, obtained with a reasonable number of parameters. To reproduce first-order phase transitions, we accounted for inter-chains interactions, treated in the mean-field approach. Hysteretic multi-step transitions, recalling experimental observations, are then achieved. Overall, the present model not only suggests new landscapes of interaction configurations between SCO molecules but also opens new avenues to tackle the complex behaviors often observed in the properties of SCO materials.

Four-Step Spin Crossover in a New Cyano-Bridged Iron-Silver Coordination Polymer.

Spin-crossover complexes with multistep transitions attract much attention due to their potential applications as multi-switches and for data storage. A four-step spin crossover is observed in the new iron(II)-based cyanometallic guest-free framework compound Fe(2-ethoxypyrazine)2 {Ag(CN)2 }2 during the transition from the low-spin to the high-spin state. A reverse process occurs in three steps. Crystallographic studies reveal an associated stepwise evolution of the crystal structures. Multiple transitions in the reported complex originate from distinct FeII sites which exist due to the packing of the ligand with a bulky substituent.