Molecular squares with paramagnetic diruthenium corners: synthetic and crystallographic challenges.
The reaction of Ru(2)(mu-O(2)CMe)(4)Cl with approximately 2.5 equiv of HDAniF (HDAniF = N,N'-di(p-anisyl)formamidine) in refluxing THF resulted in the synthesis of cis-Ru(2)(mu-DAniF)(2)(mu-O(2)CMe)(2)Cl (1). This Ru(2)(5+)complex, which has two labile acetate groups occupying two equatorial cisoid positions, was used for the construction of discrete paramagnetic supramolecular arrays. Subsequent reactions of 1 with HO(2)C-CO(2)H (oxalic acid) and 1,4-HO(2)C-C(6)H(4)-CO(2)H (terephthalic acid) followed by recrystallization from 1,2-C(2)H(4)Cl(2)/hexanes solutions containing wet MeCN or 4-Bu(t)py (4-tert-butylpyridine) gave crystals of [[is-Ru(2)(mu-DAniF)(2)Cl(H(2)O)]mu-oxalate)](4).MeCN.2(C(6)H(14)).12(H(2)O) (2) and [[is-Ru(2)(mu-DAniF)(2)Cl(0.646)(4-Bu(t)py)(1.354)]mu-terephthlate)](4)Cl(1.414).17(1,2-C(2)H(4)Cl(2)).C(6)H(14) (3), respectively. These are the first polygonal supramolecular assemblies consisting of paramagnetic M(2) units at each apex, where M(2) = Ru(2)(5+). Compounds 2 and 3 have been structurally characterized, and their electrochemistry and magnetic properties have been studied. These studies have confirmed that oxalate linkers are better than the terephthalate linkers in effecting electronic and magnetic coupling.
Angaridis
Panagiotis
P
Department of Chemistry and Laboratory for Molecular Structure and Bonding, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA.
Berry
John F
JF
Cotton
F Albert
FA
Murillo
Carlos A
CA
Wang
Xiaoping
X