1. 1.
Molecular Magnetism: Magnetic Properties of a Substituted-
Hemiporphyrazine-Tb(III) Double-Decker Sandwich Complex
Christopher Darvishian*, Christopher L. Houser
Department of Chemistry, Dr. Gordon T. Yee Group
Virginia Tech., Blacksburg, VA 24061
Recent work: Tetraaza macrocycles and
terbium complexes
Characterization: 1H NMR Spectra
Ligand Synthesis: Constructing Obu4Hp
Complexing: Forming the Double-Decker
Sandwich
Addition of Butoxy groups lends solubility and allows for characterization. Previous
Hemiporphyrazine analogues have had characterization problems due to extreme insolubility
Hemiporphyrazine: The ligand
+1.
2.
3.
EtOH
K2CO3
Reflux
w/ N2
+
CCl4
KOH
Na2S2O3
+
DMF
Reflux
+NH4
–OH
H2O
DCM
CHCl3
Hexane
4.
+
Chloronapthalene
Hemiporphyrazine
+
References:
• Hemiporphyrazines are a well known class of 32 pi-electron non-aromatic
tetraaza rings. When complexed with a metal center the ring becomes an
aromatic ligand.
• Through this aromatic character, the complex is able to exhibit novel
magnetic properties (magnetic anisotropy, hysteresis) placing the complex
under the classification of SMM
1. Gardner, T. G.; Grishina, D. A. In Towards a novel switchable aromatic hemiporphyrazine
ligand, American Chemical Society: 2013; pp ORGN-946.
• Recent work in the Yee group has produced a novel terbium
octaethyltetraazaporphyrin double-decker sandwich complex, [OETAP]3Tb2
Crystal structure of [OETAP]3Tb2 obtained by
Christopher Houser
Proposed structure of the desired
complex, (Obu4Hp)3Tb2
• The goal of the present efforts are to first synthesize Obu4Hp and
subsequently synthesize (Obu4Hp)3Tb2 double-decker sandwich complex to
collect data on its magnetic properties.
2.
3.
Stacked: