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Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties
Department of Chemistry and Biochemistry, Bayer School of Natural and Environmental Sciences, 600 Forbes Avenue, Duquesne University, Pittsburgh, PA 15282, USA
* Author to whom correspondence should be addressed.
Received: 17 August 2011; in revised form: 5 September 2011 / Accepted: 27 September 2011 / Published: 7 October 2011
Abstract: Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac)2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac)2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM)2(qox)]n·nH2O (2), trans-[Co(tmhd)2(qox)]n (3), trans-[Ni(tmhd)2(qox)]n (4), where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ) along the polymer backbone, λ = wavelength (Ǻ), A = amplitude (Ǻ), x = distance (Ǻ) along the polymer axis, provides a method to approximate and visualize the polymer structures.
Keywords: crystal engineering; wavelike polymers; sine function; wavelength; amplitude; coordination polymers
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Steward, O.W.; Kaltenbach, M.V.; Biernesser, A.B.; Taylor, M.J.; Hovan, K.J.; VerPlank, J.J.S.; Haamid, A.; Karpov, I.; Munie, M.T. Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties. Polymers 2011, 3, 1662-1672.
Steward OW, Kaltenbach MV, Biernesser AB, Taylor MJ, Hovan KJ, VerPlank JJS, Haamid A, Karpov I, Munie MT. Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties. Polymers. 2011; 3(4):1662-1672.
Steward, Omar W.; Kaltenbach, Miles V.; Biernesser, Ashley B.; Taylor, Matthew J.; Hovan, Katie J.; VerPlank, Jordan J. S.; Haamid, Ameera; Karpov, Irina; Munie, Matasebia T. 2011. "Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties." Polymers 3, no. 4: 1662-1672.