title: Spin-State Versatility in a Series of Fe4 [2 × 2] Grid Complexes: Effects of Counteranions, Lattice Solvent, and Intramolecular Cooperativity.
abstract: The new compartmental proligand 4-bromo-3,5-bis{6-(2,2'-bipyridyl)}pyrazole (HL(Br)) was synthesized and shown to form robust [2 × 2] grid complexes [Fe(II)4L(Br)4]X4 with various counteranions (X(-) = PF6(-), ClO4(-), BF4(-), Br(-)). The grid [Fe(II)4L(Br)4](4+) is stable in solution and features two high-spin (HS) and two low-spin (LS) ferrous ions in frozen MeCN, and its redox properties have been studied. Six all-ferrous compounds [Fe4L(Br)4]X4 with different counteranions and different lattice solvent (1a-f) were structurally characterized by X-ray diffraction, and their magnetic properties were investigated by Mössbauer spectroscopy and SQUID magnetometry. Variations in spin-state for the crystalline material range from the [4HS] via the [3HS-1LS] to the [2HS-2LS] forms, with some grids showing thermal spin crossover (SCO). The series of [Fe(II)4L(Br)4](4+) compounds allowed us to establish experimentally well-grounded correlations between structural distortion of the {FeN6} coordination polyhedra, quantified by using continuous shape measures, and the grid's spin-state pattern. These correlations evidenced pronounced cooperativity for the multistep SCO transitions within the grid, imparted by the strain effects of the rigid bridging ligands, and a high stability of the dimixed-spin configuration trans-[2HS-2LS] that has identical sites at opposite corners of the grid. The results are in good agreement with recent quantum chemical calculations for such molecular [2 × 2] grids featuring strongly elastically coupled vertices.
authors.affiliation: Georg-August-University , Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Steinert
authors.affiliation: Georg-August-University , Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Schneider
authors.affiliation: Georg-August-University , Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Dechert
authors.affiliation: Georg-August-University , Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Serhiy
authors.initials: S
authors.lastname: Demeshko
authors.affiliation: Georg-August-University , Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer