Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties1. Issue 1 (30th November 2015)

• Record Type: Journal Article
• Authors: Leibold, Michael; Kisslinger, Sandra; Heinemann, Frank W.; Hampel, Frank; Ichiyanagi, Yuko; Klein, Michael; Homenya, Patrick; Renz, Franz; Toftlund, Hans; Brehm, Georg; Schneider, Siegfried; Reiher, Markus; Schindler, Siegfried
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 642:Issue 1(2016)
• Page Start: 85
• Page End: 94
• Publication Date: 2015-11-30
• Subjects: Tetradentate pyridyl ligands -- Spin crossover -- LIESST effect -- Mößbauer -- Iron; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201500684
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract: Iron(II) complexes of the type [Fe(L)(NCS)2 ] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)2 ] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)2 ], [Fe(pmap)(NCS)2 ], and [Fe(tepa)(NCS)2 ] [pmea = N, N ‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N, N ‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated. Abstract :