TY - JOUR
T1 - Molecular squares with paramagnetic diruthenium corners
T2 - Synthetic and crystallographic challenges
AU - Angaridis, Panagiotis
AU - Berry, John F.
AU - Cofton, F. Albert
AU - Murillo, Carlos A.
AU - Wang, Xiaoping
PY - 2003/8/27
Y1 - 2003/8/27
N2 - The reaction of Ru2(μ-O2CMe)4Cl with ∼2.5 equiv of HDAniF (HDAniF = N,N′-di(p-anisyl)-formamidine) in refluxing THF resulted in the synthesis of cis-Ru2(μ-DAniF) 2(μ-O2CMe)2Cl (1). This RU 25+-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 2C-CO2H (oxalic acid) and 1,4-HO2C-C 6H4-CO2H (terephthalic acid) followed by recrystallization from 1,2-C2H4-Cl2/hexanes solutions containing wet MeCN or 4-Butpy (4-tert-butylpyridine) gave crystals of [{cis-Ru2(μ-DAniF)2Cl(H 2O)}(μ-oxalate)]4·MeCN·2(C 6H14)·12(H2O) (2) and [{cis-Ru 2(μ-DAniF)2Cl0.646(4-Butpy) 1.354}(μ-terephthlate)]4Cl 1.414·17(1,2-C2H4Cl 2)·C6H14 (3), respectively. These are the first polygonal supramolecular assemblies consisting of paramagnetic M 2 units at each apex, where M2 = Ru25+. 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.
AB - The reaction of Ru2(μ-O2CMe)4Cl with ∼2.5 equiv of HDAniF (HDAniF = N,N′-di(p-anisyl)-formamidine) in refluxing THF resulted in the synthesis of cis-Ru2(μ-DAniF) 2(μ-O2CMe)2Cl (1). This RU 25+-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 2C-CO2H (oxalic acid) and 1,4-HO2C-C 6H4-CO2H (terephthalic acid) followed by recrystallization from 1,2-C2H4-Cl2/hexanes solutions containing wet MeCN or 4-Butpy (4-tert-butylpyridine) gave crystals of [{cis-Ru2(μ-DAniF)2Cl(H 2O)}(μ-oxalate)]4·MeCN·2(C 6H14)·12(H2O) (2) and [{cis-Ru 2(μ-DAniF)2Cl0.646(4-Butpy) 1.354}(μ-terephthlate)]4Cl 1.414·17(1,2-C2H4Cl 2)·C6H14 (3), respectively. These are the first polygonal supramolecular assemblies consisting of paramagnetic M 2 units at each apex, where M2 = Ru25+. 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.
UR - http://www.scopus.com/inward/record.url?scp=0042932749&partnerID=8YFLogxK
U2 - 10.1021/ja036095x
DO - 10.1021/ja036095x
M3 - Article
AN - SCOPUS:0042932749
SN - 0002-7863
VL - 125
SP - 10327
EP - 10334
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 34
ER -