title: Structural and magnetic studies of two-dimensional solvent-free manganeseII complexes prepared via ligand exchange reaction under solvothermal conditions.
abstract: Systematic investigation of the ligand exchange reactions between manganese(II) acetate and benzoic acid under solvothermal conditions led to the isolation of crystalline complexes {Mn5(OC(O)CH3)6(OC(O)C6H5)4}(infinity) ( 1) and {Mn5(OC(O)CH3)4(OC(O)C6H5)6}}(infinity) ( 2) in high (i.e., >90%) yields. The complexes are characterized structurally as 2-D honeycomb-like sheets comprised of edge-shared Mn 12 loops with some noteworthy differences as follows. First, buckling of the 2-D sheet in 1 is not observed for 2, presumably as a consequence of additional intersheet phenyl groups in the latter. Second, complex 1 is comprised of only six-coordinate MnII, while 2 has both pseudo-octahedral and distorted trigonal bipyramidal coordinate metal ions. Third, while complex 2 exhibits pi-stacking interactions with intersheet phenyl-phenyl contacts of 3.285 and 3.369 A, 1 exhibits no such bonding. Antiferromagnetic exchange is observed with Weiss constants (theta) of -28 and -56 K and Neel temperatures of 2.2 and 8.2 K for complexes 1 and 2, respectively. The paramagnetic transition at higher temperatures for complex 2 may be attributed to pi-pi exchange through phenyl groups in adjacent layers. Preliminary gas sorption studies (76 K) indidate preferential adsorption of H2 versus N2 for complex 1 only.
authors.affiliation: Center for Nanoscale Science and Engineering, North Dakota State University, 1805 NDSU Research Park Drive, Fargo, North Dakota 58102, USA.
authors.forename: Shengming
authors.initials: S
authors.lastname: Liu
authors.forename: M T
authors.initials: MT
authors.lastname: Bremer
authors.forename: John
authors.initials: J
authors.lastname: Lovaasen
authors.forename: A N
authors.initials: AN
authors.lastname: Caruso
authors.forename: Kevin
authors.initials: K
authors.lastname: O'Neill
authors.forename: Lin
authors.initials: L
authors.lastname: Simpson
authors.forename: Philip A
authors.initials: PA
authors.lastname: Parilla
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Heben
authors.forename: Douglas L
authors.initials: DL
authors.lastname: Schulz