Engineering the structure and magnetic properties of crystalline solids via the metal-directed self-assembly of a versatile molecular building unit.
We report the supramolecular chemistry of several metal complexes of N-(4-pyridyl)benzamide (NPBA) with the general formula [Ma(NPBA)2AbSc], where M = Co2+, Ni2+, Zn2+, Mn2+, Cu2+, Ag+; A = NO3-, OAc-; S = MeOH, H2O; a = 0, 1, 2; b = 0, 1, 2, 4; and c = 0, 2. NPBA contains structural features that can engage in three modes of intermolecular interactions: (1) metal-ligand coordination, (2) hydrogen bonding, and (3) pi-pi stacking. NPBA forms one-dimensional (1-D) chains governed by hydrogen bonding, but when reacted with metal ions, it generates a wide variety of supramolecular scaffolds that control the arrangement of periodic nanostructures and form 1- (2-4), 2- (5), or 3-D (6-10) solid-state networks of hydrogen bonding and pi-pi stacking interactions in the crystal. Isostructural 7-9 exhibit a 2-D hydrogen bonding network that promotes topotaxial growth of single crystals of their isostructural family and generates crystal composites with two (11) and three (12) different components. Furthermore, 7-9 can also form crystalline solid solutions (M,M')(NPBA)2(NO3)2(MeOH)2 (M, M' = Co2+, Ni2+, or Zn2+, 13-16), where mixtures of Co2+, Ni2+, and Zn2+ share the same crystal lattice in different proportions to allow the formation of materials with modulated magnetic moments. Finally, we report the effects that multidimensional noncovalent networks exert on the magnetic moments between 2 and 300 K of 1-D (4), 2-D (5), and 3-D (7, 8, 10, and 13-16) paramagnetic networks.
Noveron
Juan C
JC
Department of Chemistry, University of Utah, 315 S. 1400 E. RM 2020, Salt Lake City, Utah 84112-0850, USA.
Lah
Myoung Soo
MS
Del Sesto
Rico E
RE
Arif
Atta M
AM
Miller
Joel S
JS
Stang
Peter J
PJ
D001549:Benzamides / Q000737:chemistry*; D003460:Crystallization; D006860:Hydrogen Bonding; D008280:Magnetics; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D013329:Structure-Activity Relationship
D001549:Benzamides; D008670:Metals; C462062:N-(4-pyridyl)benzamide; D009942:Organometallic Compounds