Spectroscopic and energetic properties of thorium(IV) molecular clusters with a hexanuclear core

The spectral and energetic properties of three polynuclear thorium(IV) molecular complexes Th(6)(OH)(4)O(4)(H(2)O)(6)(HCOO)(12)·nH(2)O (1), Th(6)(OH)(4)O(4)(H(2)O)(6)(CH(3)COO)(12)·nH(2)O (2), and Th(6)(OH)(4)O(4)(H(2)O)(6)(ClCH(2)COO)(12)·4H(2)O (3) have been studied. Each complex has a hexanuclear core with six 9-coordinate Th(IV) cations bridged by four μ(3)-hydroxo and four μ(3)-oxo groups. The +12 core is stabilized by twelve bridging carboxylate functionalized organic acid (formate, acetate, and chloroacetate) units. The calculated (1)H NMR chemical shifts for the four μ(3)-hydroxo, water, and formate protons are reported and compared to the experimental values. The vibrational frequencies were calculated to aid in the assignment of the observed Raman bands. The Mulliken and NBO (natural bond orbital) charges are calculated for the Th clusters. The Th atoms are positive and the bridging O and O(H) are negative. The analysis of the calculated highest-occupied and lowest-unoccupied molecular orbitals (HOMO and LUMO) is reported. The average water complexation energies, the gas phase, the aqueous and dimethylsulfoxide (DMSO) acidities were predicted, and the Th clusters are found to be mild to strong acids in gas phase yet they behave as weak acids in solution.