Structures and properties of large supramolecular coordination complexes predicted with the generalized energy-based fragmentation method.

Abstract

The generalized energy-based fragmentation (GEBF) method has been extended to facilitate ab initio calculations of large supramolecular coordination complexes. For metal-containing coordination complexes, a special fragmentation scheme is proposed for GEBF calculations, in which coordinate bonds between metal ions and ligands are kept intact, and only single covalent bonds in organic ligands are cut into fragments. A simple strategy is exploited for the determination of the ground-state spin multiplicity of each metal ion so that the total spin of all metal-containing subsystems is assigned automatically. With this fragmentation scheme, the GEBF method is demonstrated to provide reliable energies, optimized geometry, nuclear magnetic resonance (NMR) properties and the infrared spectrum for a medium-sized supramolecular coordination complex, which are very consistent with those from the full-system quantum chemistry calculations. The GEBF method is then applied to two large supramolecular coordination complexes to illustrate its capability. For the trimetallic coordination complex Fe2Zn2(RuL2)2 (with 618 atoms), the calculated 1H chemical shifts from GEBF calculations with the B97-2 functional can account well for the experimental NMR spectrum. For the cage-guest complex Pd4L8(BF4-)3, the computed infrared spectrum obtained with the GEBF-M06-2X method can help assign the experimental peaks to the corresponding vibrational motions. The GEBF method combining with advanced electronic structure methods is expected to be a useful tool to understand and interpret structural and spectroscopic information of various supramolecular coordination complexes.