Influence of the Substituted Side Group on the Molecular Structure and Electronic Properties of TPP and Related Implications on Organic Zeolites Use

Abstract

Tris(o-phenylenedioxy)cyclotriphosphazene (TPP) became a compound of choice to investigate the structural features of organic zeolite and their potential applications. Different TPP-like materials are studied in this Letter from the electron-donor (E-D) capacity viewpoint, since this was reported as a stabilizing parameter of the TPP-Lewis acid inclusion compound up to high temperatures. On the basis of DFT-PBE0/6-31G(d,p) calculations, the results reported herein show a tight dependence of the E-D of the entire molecule on that of the side group. It was shown that both the O/NH substitution and the extension of the phenylenedioxyl group with an aromatic ring significantly enhance the E-D. As a result, the corresponding clathrates, including some reported ones, may also be exploited for the same issue, with an even wider range of operating temperatures when trapping compounds of Lewis acidity character comparable to that of I2. Furthermore, it was concluded that these two strategies may significantly enhance the E-D capacity without altering the tolerance of TPP-like host materials to the guest molecules.

Preparation and Characterization of New Inclusion Compounds Using Stable Nitroxide Radicals and an Organic 1-D Nanochannel as a Template

“…This is even the case for TPP/benzene IC, in which the shape of guest molecules is simple and highly symmetric [16,17,18,19,20]. In addition, TPP is also a medium for gas storage because the strong affinity of the wall of the nanochannels makes it possible to include even gas molecules [21,22,23]. …”

The Design of Tris(o-phenylenedioxy)cyclo-trisphosphazene (TPP) Derivatives and Analogs toward Multifunctional Zeolite Use

“…Our preliminary calculations have proved that based on Koopman`s theory, the HF/6-311+G* can yield an excellent accuracy for adiabatic IP [16]. …”

“…We focused our interest on the relationship between the E-D capacity of the side fragment (part C), bridge (part B), and that for the entire molecule. Although a number of theoretical works on phosphazene containing systems can be found in the literature [15,16], very few were devoted to related OZ and the relationship between E-D and the structure of molecules [16]. This contribution may provide some helpful insights toward the understanding of TPP-like OZ uses and the further design as well.…”

Self‐Organization by Chiral Recognition Based on ad hoc Chiral Pockets in Cyclotriphosphazenes with Binaphthoxy and Biphenoxy Substituents: An X‐ray, NMR and Computational Study

“…Spirocyclic phosphazenes are of particular interest because of their ability to act as host molecules,9 as well as to induce inclusion polymerization 10. Recent calculations on tris( o ‐phenylenedioxy)cyclotriphosphazene and related cycles have shown that the electron‐donating capacity of the entire molecule is very dependent on that of the side‐group11 and that good electron‐donating capacity and the paddle wheel molecular shape make them good candidates for organic superconductors 12…”