Insertion of Dipolar Molecules in Channels of a Centrosymmetric Organic Zeolite: Molecular Modeling and Experimental Investigations on Diffusion and Polarity Formation
- 24 March 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 109 (16) , 7961-7968
- https://doi.org/10.1021/jp044464l
Abstract
The mechanism of insertion of p-nitroaniline (PNA) and its diffusion behavior in channels of the hexagonal host structure of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) was investigated by means of molecular modeling tools. Strong preferential sites in the bulk were found to be due to π−π and NH−π interactions between PNA and channel walls of TPP. MD simulations showed that diffusion can be characterized by jumps from one site to the next, occurring mainly because of the dynamic flexibility of the host structure. Calculations of host−guest interactions between the TPP surface and PNA approaching the entrance of channels with its terminal H2N-first or O2N-first revealed that the H2N-first insertion is clearly preferred. Preferential insertion of PNA is found to be the reason for polar effects, observed experimentally. Because of a distinct guest−host recognition at the surface, guest−guest interactions were found to have a minor influence on polarity.Keywords
This publication has 17 references indexed in Scilit:
- Prediction of Growth-Induced Polarity in Centrosymmetric Molecular Crystals Using Force Field MethodsChemistry of Materials, 2004
- A Family of Supramolecular Frameworks of Polyconjugated Molecules Hosted in Aromatic NanochannelsAngewandte Chemie International Edition in English, 2004
- Self-diffusion of n-alkanes in silicalite using molecular dynamics simulation: A comparison between rigid and flexible frameworksPhysical Chemistry Chemical Physics, 2004
- Ising model of polarity formation in molecular crystals: From the growth model to the asymptotic equilibrium statePhysical Review E, 2002
- Supramolecular-Wire Confinement of I2 Molecules in Channels of the Organic Zeolite Tris(o-phenylenedioxy)cyclotriphosphazeneAngewandte Chemie International Edition in English, 2002
- The crystallization of polar, channel‐type inclusion compounds: Property‐directed superamolecular synthesisAdvanced Materials, 1997
- Model for growth of binary alloys with fast surface equilibrationPhysical Review E, 1997
- Polar inclusion compounds of perhydrotriphenylene (phtp) and efficient nonlinear optical molecules**Advanced Materials, 1995
- Surface-induced ordering in GaInPPhysical Review Letters, 1991
- Preparation of six- and eight-membered mixed cyanuric-thiazyl rings, (R2NCN)x(NSCl)2 (x = 1,2) and the x-ray crystal structure of (Et2NCN)(NSCl)2Inorganic Chemistry, 1986