This document summarizes recent work synthesizing a substituted-hemiporphyrazine-Tb(III) double-decker sandwich complex and characterizing its magnetic properties. It first reviews previous work with tetraaza macrocycles and terbium complexes. It then outlines the ligand synthesis, complex formation, and characterization of the new complex. The goal is to add butoxy groups to improve solubility and study the magnetic properties of the substituted complex.

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: