TY - JOUR
T1 - Reversible and irreversible vapor-induced guest molecule exchange in spin-crossover compounds
AU - Wei, Rong Jia
AU - Tao, Jun
AU - Huang, Rong Bin
AU - Zheng, Lan Sun
PY - 2011/9/5
Y1 - 2011/9/5
N2 - Spin-crossover (SCO) complex [Fe(tpa)(NCS)2] (tpa = tri(2-pyridylmethyl)amine) crystallized in two solvate forms, yellow [Fe(tpa)(NCS)2]·X [Fe:X = 1:1; X = n-PrOH (complex is named as n-PrOH), i-PrOH (i-PrOH), CH2Cl2 (CH2Cl 2), CHCl3 (CHCl3), MeCN (MeCN)] and red [Fe(tpa)(NCS)2]2·Y [Fe:Y = 2:1; Y = MeOH (MeOH), EtOH (EtOH)], respectively. Between the two forms, interesting solvent-vapor induced in situ reversible and irreversible guest molecule exchanges, [Fe(tpa)(NCS)2]·X → [Fe(tpa)(NCS)2] 2·Y, occurred in the solid state followed by dramatic color changes as well as distinct structural and SCO behavior transformations. Comprehensive studies on structures and SCO behaviors associating guest exchanges have been conducted by X-ray single-crystal diffraction, PXRD, IR, elemental analysis, and magnetic measurements, respectively. This discrete molecular system shows unique solvent-dependent SCO behavior related to the nature of solvent molecules; the distinct color changes during guest exchange originate from the alternations of electronic states of the guest-sensitive FeII centers, providing an effective route to fine-tune and optimize materials properties by systematic structural perturbation, or serving for detection of toxic gases, such as CH2Cl2 and CHCl 3.
AB - Spin-crossover (SCO) complex [Fe(tpa)(NCS)2] (tpa = tri(2-pyridylmethyl)amine) crystallized in two solvate forms, yellow [Fe(tpa)(NCS)2]·X [Fe:X = 1:1; X = n-PrOH (complex is named as n-PrOH), i-PrOH (i-PrOH), CH2Cl2 (CH2Cl 2), CHCl3 (CHCl3), MeCN (MeCN)] and red [Fe(tpa)(NCS)2]2·Y [Fe:Y = 2:1; Y = MeOH (MeOH), EtOH (EtOH)], respectively. Between the two forms, interesting solvent-vapor induced in situ reversible and irreversible guest molecule exchanges, [Fe(tpa)(NCS)2]·X → [Fe(tpa)(NCS)2] 2·Y, occurred in the solid state followed by dramatic color changes as well as distinct structural and SCO behavior transformations. Comprehensive studies on structures and SCO behaviors associating guest exchanges have been conducted by X-ray single-crystal diffraction, PXRD, IR, elemental analysis, and magnetic measurements, respectively. This discrete molecular system shows unique solvent-dependent SCO behavior related to the nature of solvent molecules; the distinct color changes during guest exchange originate from the alternations of electronic states of the guest-sensitive FeII centers, providing an effective route to fine-tune and optimize materials properties by systematic structural perturbation, or serving for detection of toxic gases, such as CH2Cl2 and CHCl 3.
UR - http://www.scopus.com/inward/record.url?scp=80052238289&partnerID=8YFLogxK
U2 - 10.1021/ic201142t
DO - 10.1021/ic201142t
M3 - Article
AN - SCOPUS:80052238289
SN - 0020-1669
VL - 50
SP - 8553
EP - 8564
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 17
ER -