Theoretical calculation and prediction for experimental design to obtain spin crossover complexes |
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| Authors: | Farsheed Shahbazi‐Raz Maryam Adineh Nasser Safari Mansour Zahedi |
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| Institution: | Department of Chemistry, Shahid Beheshti University, Tehran, Iran |
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| Abstract: | DFT methods were utilized to study SCO complexes. Fe(2btz)2(NCX)2] (2btz = 2,2′‐bithiazoline, X = S ( 1 ) and Se ( 2 )), Fe(phen)2(NCX)2] (phen = 1,10‐phenantroline, X = S ( 3 ) and Se ( 4 )), and Fe(bpy)2(NCS)2] ( 5 ) (bpy = 2,2′‐bipyridine) compounds, which have experimentally shown SCO behavior, were calculated. B3LYP, B3LYP*, OPBE, and OLYP with 6‐31G* and 6‐311 + G** basis sets were employed to calculate the ΔEHS/LS energy gap as a clue to find complexes with SCO behavior. It is found that calculated result by B3LYP* with c3 = 0.14 and OPBE methods and 6‐31G* basis set are in agreement with experimentally observed SCO complexes. Then, newly designed Fe(N‐N)2(X)2 complexes, where N‐N are bidentate nitrogen donor chelating ligands and X= SCN‐, SeCN‐, Cl‐, Br‐, I‐,  were chosen to see their potential to be SCO compounds. ΔEHS/LS for potential SCO complexes are estimated from 0.8 to 6.5 kcal/mol in B3LYP* and 0.6–5.7 kcal/mol in OPBE. These calculations suggest Fe(bpy)2(NCSe)2], Fe(5dmbpy)2(NCS)2], and Fe(3‐BrPhen)2(NCSe)2] compounds have the ability to show SCO behavior. © 2016 Wiley Periodicals, Inc. |
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| Keywords: | spin crossover DFT calculation basis set energy gap high spin low spin Fe(II) complexes |
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