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Updated: Apr 14, 2026
Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain
Published on: March 27, 2018
Solvent-Regulated Lattice Elasticity and Pressure-Induced Multi-Stimuli Spin-State Bistability in a Porous Hexagonal
Krishna Kaushik1, Pradip Kumar Mondal2, Sujit Kamilya1
1Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, India.
Abstract:
Spin-state switching in molecular materials becomes most effective when multiple external stimuli converge on a common structural pathway. Here we report a porous cyanide-bridged {4d-3d} heterobimetallic framework formulated as {[Mo(CN)8][Fe(v-im)4]2(BF4).2DMF.H2O}n (1·2DMF·H2O) (v-im = 1-vinylimidazole). Single-crystal x-ray diffraction reveals a flexible 3D hexagonal network where [Mo(CN)8]3 - units mediate magnetic communication through [Fe(v-im)4] nodes. Partial desolvation generates an elastic lattice (1·2DMF) that exhibits reversible thermally induced spin-state switching with T1/2 = 127 K and a pronounced light-induced excited spin-state trapping (LIESST) effect at TLIESST = 60 K. In contrast, the fully solvated framework (1·2DMF·H2O) remains HS at ambient conditions, but switches under hydrostatic pressure, demonstrating structural matrix-, stress- and squeeze-driven bistability. The cooperative response originates from dynamic coupling between solvent molecules, counter-ions, and the flexible framework, which collectively tune the spin-state energetics. This study establishes elastic-matrix squeezing as a unifying strategy for multi-stimuli bistability and highlights the convergence of porosity, elasticity, and spin-crossover behavior in adaptive molecular frameworks.
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