Hydroxo-bridged dimers of oxo-centered ruthenium(III) triangle: synthesis and spectroscopic and theoretical investigations.
The homometallic hexameric ruthenium cluster of the formula [Ru(III)6(μ3-O)2(μ-OH)2((CH3)3CCO2)12(py)2] (1) (py = pyridine) is solved by single-crystal X-ray diffraction. Magnetic susceptibility measurements performed on 1 suggest that the antiferromagnetic interaction between the Ru(III) centers is dominant, and this is supported by theoretical studies. Theoretical calculations based on density functional methods yield eight different exchange interaction values for 1: J1 = -737.6, J2 = +63.4, J3 = -187.6, J4 = +124.4, J5 = -376.4, J6 = -601.2, J7 = -657.0, and J8 = -800.6 cm(-1). Among all the computed J values, six are found to be antiferromagnetic. Four exchange values (J1, J6, J7 and J8) are computed to be extremely strong, with J8, mediated through one μ-hydroxo and a carboxylate bridge, being by far the largest exchange obtained for any transition-metal cluster. The origin of these strong interactions is the orientation of the magnetic orbitals in the Ru(III) centers, and the computed J values are rationalized by using molecular orbital and natural bond order analysis. Detailed NMR studies ((1)H, (13)C, HSQC, NOESY, and TOCSY) of 1 (in CDCl3) confirm the existence of the solid-state structure in solution. The observation of sharp NMR peaks and spin-lattice time relaxation (T1 relaxation) experiments support the existence of strong intramolecular antiferromagnetic exchange interactions between the metal centers. A broad absorption peak around 600-1000 nm in the visible to near-IR region is a characteristic signature of an intracluster charge-transfer transition. Cyclic voltammetry experiments show that there are three reversible one-electron redox couples at -0.865, +0.186, and +1.159 V with respect to the Ag/AgCl reference electrode, which corresponds to two metal-based one-electron oxidations and one reduction process.
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra 400 076 (India), Fax: (+91) 22-2576-7152.
Apoorva
A
Upadhyay
Jitendrasingh
J
Rajpurohit
Mukesh
M
Kumar Singh
Richa
R
Dubey
Anant Kumar
AK
Srivastava
Ashutosh
A
Kumar
Gopalan
G
Rajaraman
Maheswaran
M
Shanmugam
D018360:Crystallography, X-Ray; D019281:Dimerization; D009682:Magnetic Resonance Spectroscopy; D059346:Magnets / Q000737:chemistry; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
D011725:Pyridines; D012428:Ruthenium; C023666:pyridine; D010100:Oxygen
NMR spectroscopy; cluster compounds; density functional calculations; magnetism; ruthenium