Alcohol effects in a series of iron(III)spin crossover complexes[Fe(qsal-Cl)_(2)]NO_(3)·ROH(R=Me 1,Et 2,1-Pr 3)are explored.Despite the solvents differing from each other by only one or two CH_(2) groups,unique p...Alcohol effects in a series of iron(III)spin crossover complexes[Fe(qsal-Cl)_(2)]NO_(3)·ROH(R=Me 1,Et 2,1-Pr 3)are explored.Despite the solvents differing from each other by only one or two CH_(2) groups,unique packing motifs are observed for each complex.While 1 crystallizes in triclinic P[1 with combining macron]with two independent iron(III)centres,connecting them in a tight undulating 1D chain with a rectangular cross-section,2(monoclinic P2_(1)/c)and 3(monoclinic I2/a)crystallize with only one iron center.For 2,a linear 1D chain is observed with a square cross-section,while 3 exhibits a looser 1D chain formed by dimers.The 3D supramolecular networks are distinctive with 1 showing identical parallelogram shaped 2D sheets,whereas 2 and 3 show alternating 2D sheets with differing staggering between the layers(AB).These results are supported by Hirshfeld surface analysis.The magnetic studies show no significant SCO for 1 and 3.However,2 shows an incomplete gradual spin transition(T_(1/2)=200 K).Moreover,upon partial ethanol desolvation,a 25 K hysteresis near room temperature(T_(1/2)↓=275 K,T_(1/2)↑=300 K)is observed.The packing observed in 2 is present in many other[Fe(qsal-X)2]+complexes with hysteresis and abrupt SCO.DFT calculations using the r^(2)SCAN functional quantify the differences for 1 and 2 in the low-high spin energy and their cooperative effects.This study illustrates that even small changes in the solvent can dramatically influence the crystal packing and therefore the SCO properties.展开更多
基金the National Research Council of Thailand(NRCT)grant number NRCT5-RSA63019-02the Thailand Science Research and Innovation Fund(Contract No.FRB650082/227)for funding+2 种基金The National Science Technology and Innovation Policy Office for Integrated Research and Innovation Plan(Grant No.256113A3050001)is thanked for funds to purchase an X-ray diffractometerVidyasirimedhi Institute of Science and Technology is thanked for elemental analysisthe Spanish Ministerio de Ciencia e Innovación(PGC2018-093863-B-C21 and MDM-2017-0767)。
文摘Alcohol effects in a series of iron(III)spin crossover complexes[Fe(qsal-Cl)_(2)]NO_(3)·ROH(R=Me 1,Et 2,1-Pr 3)are explored.Despite the solvents differing from each other by only one or two CH_(2) groups,unique packing motifs are observed for each complex.While 1 crystallizes in triclinic P[1 with combining macron]with two independent iron(III)centres,connecting them in a tight undulating 1D chain with a rectangular cross-section,2(monoclinic P2_(1)/c)and 3(monoclinic I2/a)crystallize with only one iron center.For 2,a linear 1D chain is observed with a square cross-section,while 3 exhibits a looser 1D chain formed by dimers.The 3D supramolecular networks are distinctive with 1 showing identical parallelogram shaped 2D sheets,whereas 2 and 3 show alternating 2D sheets with differing staggering between the layers(AB).These results are supported by Hirshfeld surface analysis.The magnetic studies show no significant SCO for 1 and 3.However,2 shows an incomplete gradual spin transition(T_(1/2)=200 K).Moreover,upon partial ethanol desolvation,a 25 K hysteresis near room temperature(T_(1/2)↓=275 K,T_(1/2)↑=300 K)is observed.The packing observed in 2 is present in many other[Fe(qsal-X)2]+complexes with hysteresis and abrupt SCO.DFT calculations using the r^(2)SCAN functional quantify the differences for 1 and 2 in the low-high spin energy and their cooperative effects.This study illustrates that even small changes in the solvent can dramatically influence the crystal packing and therefore the SCO properties.
