Design of Tetrathiafulvalene-Based Phosphazenes Combining a Good Electron-Donor Capacity and Possible Inclusion Adduct Formation (Part II)

Abstract

Physical properties of intercalated porous material can be modulated by intercalation of small molecules, as this was demonstrated through the iodine (I2) intercalation into tris(o-phenylenedioxy)cyclotriphosphazene (TPP) crystals. This work describes in depth theoretical considerations of TPP derivatives. The core ring [(NP)3] substitution by [(CO)3], [(CNH)3], and [(CS)3], as well as the side group modification in size and composition (containing tetrathiafulvalene-like fragments), is well described from the most important aspects as their geometry optimization, their highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) consideration together with ionization potentials (IP), and their charged forms. On the basis of PBE0/6-31G(d,p) calculations, the neutral forms of the [(CO)3], [(CNH)3], and [(CS)3] containing derivatives are predicted in a distorted caplike conformation. In the first two series, planar (or nearly planar) conformations are predicted upon oxidation, while ...