Magnetic, Structural and Spectroscopic Properties of Iron(II)-Octacyanoniobate(IV) Crystalline Film Obtained by Ion-Exchange Synthesis

Sas, Wojciech; Pinkowicz, Dawid; Perzanowski, Marcin; Fitta, Magdalena

doi:10.3390/ma13133029

Cited by 3 publications

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“…The films microstructure compares favorably to that of the films obtained from related CN‐bridged networks. The films obtained from suspension show smaller grain size and better surface evenness in comparison to PBAs obtained by electrochemical deposition, [ 24 ] the Fe II ‐Nb IV based network obtained by ion‐exchange [ 41 ] and the Fe II ‐Pt II Hoffman‐type network obtained by pulsed laser evaporation. [ 38 ] The morphology of the films obtained by sequential growth is similar to that of the films obtained by the same method from PBAs [ 33 ] and Hoffman‐type networks.…”

Section: Resultsmentioning

confidence: 99%

“…Deposition of hybrid organic-inorganic CN-bridged networks, apart from isolated reports, is a practically unexplored area. [38][39][40][41] Numerous earlier studies on other molecular magnets, particularly those devoted to anchoring SMMs on surfaces, have shown that magnetic properties are easily influenced by both reduction of the particle size as well as interface interactions with the substrate. [42][43][44] Therefore, in order to employ solvatomagnetic properties in the construction of chemo-sensitive switches it is essential to investigate if the properties of the bulk material are retained in thin films.…”

Section: Introductionmentioning

confidence: 99%

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Thin Films of Solvatomagnetic CN‐Bridged Coordination Polymers: From Micro to Nanoscale

Pacanowska

Fitta

Kozieł

et al. 2022

Adv Materials Inter

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Cyano-bridged coordination polymers constitute an important group of molecule-based magnets. [12][13][14] The CN-bridges mediate relatively strong magnetic interactions and at the same time they allow reasonable control over the self-assembly process and thus the rational design of versatile topologies by the use of appropriate blocking ligands. Moreover, the CN-bridges are robust but bendable, which may give rise to framework flexibility and structural transformations triggered by desolvation or sorption of small molecules. Since the sign and magnitude of magnetic superexchange for many metal ions depend on the geometry of the CN-bridges, the structurally flexible networks often show sorption-driven changes in magnetic characteristics. Porosity is not common in CN-bridged polymers, since the CN-ligands are relatively short. However, it can be introduced by the use of additional long organic bridging ligands or pre-defined complex building blocks acting as linear linkers. Following the later approach, by using Ni II with equatorial positions blocked by the cyclam ligand (cyclam = 1,4,7,11-tetraazacyclotetradecane), a family of microporous 2D networks of characteristic honeycomblike topology, based on hexa-or octa-cyanometallates have been obtained. [15][16][17] Although these coordination polymers do not contain any coordinated solvent molecules, they show unusually rich solvatomagnetic effect, connected with sorption of guest solvent molecules, like water or methanol, into the microporous channels. The structural transformations upon guest inclusion are restricted to changes in bond geometry and the deformation of the coordination skeleton, which retains its original topology. However, even these relatively small structural changes cause marked differences in magnetic properties between different pseudopolymorphic forms. [18] Two isostructural {[Ni II (cyclam)] 3 [M III (CN) 6 ] 2 •nH 2 O}n (M = Cr or Fe) networks proved to be particularly robust and were characterized as two different hydrates and an anhydrous form, with fully reversible interconversion pathways between them. [19] In view of potential applications of the solvatomagnetic effect we decided to find effective methods of surface deposition for the above mentioned networks and investigate if their properties are retained in thin films.Preparation of molecule-based magnetic materials in the form of thin films is an important step toward exploration of their application potential. [20] Compounds in the form of thin films react more efficiently to external stimuli and are more suitable for the construction of molecular devices. Several Two types of thin films differing in thickness and morphology of microporous CN-bridged hybrid organic-inorganic {[Ni II (cyclam)] 3 [M III (CN) 6 ] 2 •nH 2 O}n (M = Cr or Fe, cyclam = 1,4,7,11-tetraazacyclotetradecane) coordination networks are obtained by using physical and chemical deposition techniques. By adsorption on the PET/ITO substrate of the pre-formed nano-sized crystallites from water suspension, films of 1-2...

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