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Updated: Aug 6, 2026

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Dynamic equilibrium between cyclic oligomers. Thermodynamic and structural characterization of a square and a
F Albert Cotton1, Carlos A Murillo, Rongmin Yu
1Department of Chemistry and Laboratory for Molecular Structure and Bonding, P. O. Box 3012, Texas A and M University, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Abstract:
A dynamic equilibrium has been found in CDCl3 between a neutral molecular square, [cis-Mo2(DAniF)2]4(O2CC6F4CO2)4 (1) and triangle, [cis-Mo2(DAniF)2]3(O2CC6F4CO2)3 (2) (DAniF = the anion of N,N'-di-p-anisylformamidine). The two components have been crystallographically characterized and solution studies by 1H and 19F NMR spectra of the concentration- and the temperature-dependence of the equilibrium have been performed. The conversion of three moles of molecular squares 1 to four moles of molecular triangles 2 has an equilibrium constant of 1.98(7) x 10(-4) at 23.7 degrees C. At this temperature, the DeltaG(0) for the conversion of three moles of squares to four moles of triangles is 21.0 kJ mol(-1). The conversion is enthalpically disfavored (DeltaH(0) = 23.5 kJ mol(-1)), but entropically favored (DeltaS(0) = 8.2 J K(-1) mol(-1)).
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