Metastable phases of the photoswitchable molecular magnet K0.3Co[Fe(CN)6]0.77 ⋅ nH2O in sub-micrometer particles have been structurally investigated by synchrotron powder x-ray diffraction (PXRD) measurements. The K0.3Co[Fe(CN)6]0.77 ⋅ nH2O bulk compound (studied here with a sample having average particle size of 500 nm) undergoes a charge transfer coupled spin transition (CTCST), where spin configurations change between a paramagnetic CoII( S = 3/2) –FeIII( S = 1/2) high-temperature (HT) state and a diamagnetic CoIII( S = 0) –FeII( S = 0) low-temperature (LT) state. The bulk compound exhibits a unique intermediate (IM) phase, which corresponds to a mixture of HT and LT spin states that depend on the cooling rate. Several hidden metastable HT states emerge as a function of thermal and photo stimuli, namely: (1) a quench (Q) state generated from the HT state by flash cooling, (2) a LTPX state obtained by photoexcitation from the LT state derived by thermal relaxation from the Q state, and (3) an IMPX state accessed by photo-irradiation from the IM state. A sample with a smaller particle size, 135 nm, is investigated for which the particles are on the scale of the coherent LT domains in the IM phase within the larger 500 nm sample. PXRD studies under controlled thermal and/or optical excitations have clarified that the reduction of the particle size profoundly affects the structural changes associated with the CTCST. The unusual IM state is also observed as segregated domains in the 135 nm particle, but the collective structural transformations are more hindered in small particles. The volume change decreases to 2%–3%, almost half the value found for 500 nm particles (5%–8%), even though the linear thermal expansion coefficients are larger for the smaller particles. Furthermore, photoexcitation from the IM and LT states does not turn into single phases in the smaller particles, presumably because of the multiple interfaces and/or internal stress generated by the coexistence of small CoII–FeIIIand CoIII–FeIIdomains in the lattice. Since the reduced particle size limits cooperativity and domain growth in the lattice, CTCST in the small particle sample becomes less sensitive to external stimuli.
Interplay between core and shell in a RbCoFe@RbNiCo Prussian blue analogue spin transition heterostructure
A series of core–shell heterostructures consisting of the spin transition Prussian blue analogue Rb a Co b [Fe(CN) 6 ] c · m H 2 O (RbCoFe–PBA) as core with different shell thicknesses of K j Ni k [Co(CN) 6 ] l · n H 2 O (KNiCo-PBA) has been prepared and studied as the cores undergo both thermal and light-induced phase changes. Synchrotron powder diffraction and SQUID magnetometry indicate the intersite cooperativity of the charge transfer coupled spin transition (CTCST) in the RbCoFe–PBA core decreases while the extent of lattice contraction is reduced relative to the uncoated particles. Isothermal relaxation measurements from the photo-induced high-spin (HS) state to the low-spin (LS) ground state of the RbCoFe–PBA core show that the energy barrier of the HS to LS transition dramatically decreases when adding the KNiCo-PBA shells, becoming smaller when the shell is thicker. The RbCoFe–PBA@KNiCo-PBA series is unique because the lattice parameter of KNiCo-PBA grown on the high-spin RbCoFe–PBA core particle is expanded relative to its equilibrium lattice parameter. As a result, the lattice mismatch is relieved during the spin transition. Analysis of the structural microstrain in both core and shell during the CTCST process reveals the different mechanisms by which the heterostructure accommodates the strain.
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- NSF-PAR ID:
- 10283101
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- ISSN:
- 2050-7526
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1TC01514A
