A thermal- and light-induced switchable one-dimensional rare loop-like spin crossover coordination polymer

Rare loop-like isostructural one-dimensional coordination polymer (1D-CP) systems formulated as {Fe(DPIP) 2 (NCSe) 2 } n 4DMF ( 1 ) and {Fe(DPIP) 2 (NCSe) 2 } n 4DMF ( 2 ) were obtained by self-assembling Fe II and pseudohalide NCX (X = S, Se) ions in presence of the V-shaped bidentate bridging liga...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-12, Vol.48 (45), p.1714-1721
Main Authors: Lan, Wenlong, Valverde-Muoz, Francisco Javier, Dou, Yong, Hao, Xiaoyun, Muoz, M. Carmen, Zhou, Zhen, Liu, Hui, Liu, Qingyun, Real, Jos Antonio, Zhang, Daopeng
Format: Article
Language:English
Subjects:
Chemical analysis
Coordination polymers
Crystallography
Electron spin
Homology
Hydrogen bonds
Hysteresis loops
Infrared analysis
Infrared spectroscopy
Ligands
Magnetic properties
Single crystals
Spectrum analysis
X ray powder diffraction
X-ray diffraction
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Summary:Rare loop-like isostructural one-dimensional coordination polymer (1D-CP) systems formulated as {Fe(DPIP) 2 (NCSe) 2 } n 4DMF ( 1 ) and {Fe(DPIP) 2 (NCSe) 2 } n 4DMF ( 2 ) were obtained by self-assembling Fe II and pseudohalide NCX (X = S, Se) ions in presence of the V-shaped bidentate bridging ligand, namely, N , N -dipyridin-4-ylisophthalamide (DPIP), and were characterized by elemental analysis, IR spectroscopy, TGA, single crystal X-ray diffraction and powder X-ray diffraction. The magnetic studies show that complex 2 undergoes a complete thermally induced spin crossover (SCO) behavior centered at T 1/2 = 120 K with ca. 5 K thermal hysteresis loop and light-induced excited spin state trapping effect (LIESST) with T LIESST = 65 K. However, either the homologous X = S ( 1 ) or the desolvated form of complex 2 is high spin at all temperatures, proving further the concerted synergy for the SCO of 2 between the intrinsic ligand field and that indirectly induced via hydrogen bond interaction. The current results provide valuable information for the design of new 1D SCO systems via the rational control of the cooperated effects derived from the intramolecular coordination bond and the intermolecular supramolecular interactions. The looped-like 1D coordination polymer {Fe(DPIP) 2 (NCSe) 2 } n 4DMF displays a thermal and light spin crossover behavior strongly dependent on the occurrence of intermolecular hydrogen bonds between the ligand amide functions and the solvent molecules.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03285a