The Real Time Flipping Dynamics Studies of Dipolar Diflourophenylene Rotator (Compass Needle) of Crystalline Siloxaalkane Molecular Compass

Anant Babu Marahatta

Abstract


One of the most indispensable strategies of nanotechnology is to integrate the networks of molecular arrays and their explicit functionalizable physicochemical properties of those type crystalline materials that exhibit unique amphidynamic behavior at wide range temperature regimes, and respond genuinely to the external stimuli owing to the inventions of smart, and intelligent nanomachines. The recently synthesized macroscopic compass like macrocyclic crystalline compound with a completely closed structural topology possessing a Si-C spin axis, and a dipolar diflourophenylene (rotator) ring encapsulated into the peripheral -(Si-O)x- & -Si-O-Si- made siloxaalkane spokes (stator) is one of such type materials whose central rotator is experimentally observed as 1p-flipped in two degenerate positions (b and b') at T = 273 K. Herein, all the associated rotary dynamical assets of this gyrotop molecular arrays are probed under crystalline conditions by employing the NCC-DFTB/MD simulation scheme. The general results achieved in this study are found to justify the X-ray/1H-NMR predicted flipping motions and temporal behavior of the central dipolar rotator in real-time scales. When the average kinetic temperatures T of the molecular ensemble are set to 1200 K & 600 K, the rotator is found to consume @8 ps & @45 ps with the flipping rates of  = 0.022 ps-1 &  = 0.125 ps-1 respectively for the specific b®b' 1p-flipping, but when T is reduced to 273 K, this flipping motion is completely forbidden within the present simulation timeframe of £ 200 ps. The flipping barrier value Ea = 4.3 kcal/mol obtained from the Arrhenius equation is also found to lie in well agreeable range to that determined through the Gaussian-external PES techniques (Ea = 4.9 kcal/mol). The results presented here are quite essential to understand the compass/gyroscope like functions of the siloxaalkane molecular analogues which in turn speculate their functionalizing masterplans comprehensively.

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DOI: http://dx.doi.org/10.52155/ijpsat.v45.1.6172

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