Molecular Complexes of Diethyl N,N′-1,3-Phenyldioxalamate and Resorcinols: Conformational Switching through Intramolecular Three-Centered Hydrogen-Bonding
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- 作者：Juan Saulo González-González ; Francisco J. Martínez-Martínez ; Efrén V. García-Báez ; Alejandro Cruz ; Luis M. Morín-Sánchez ; Susana Rojas-Lima ; Itzia I. Padilla-Martínez
- 刊名：Crystal Growth & Design
- 出版年：2014
- 出版时间：February 5, 2014
- 年：2014
- 卷：14
- 期：2
- 页码：628-642
- 全文大小：893K
- ISSN：1528-7505
文摘
The mechanochemically induced complexation between diethyl N,N鈥?1,3-phenyldioxalamate tweezers and resorcinol, orcinol, 4,6-di-tert-butyl-1,3-benzenediol, and 4-hexyl-1,3-benzenediol is described. IR-spectroscopy, X-ray powder diffraction, <sup>13sup>C CPMAS, and single X-ray diffraction allowed establishing the structures of the complexes as hydrogen-bonded heterodimers and heterotetramers. Complexation occurs through O鈥揌路路路O鈺怌 hydrogen-bonding interactions with the participation of phenolic OH and amide carbonyl groups. The initial conformation and steric factors coming from the 1,3-benzenediols exert a strong influence on the final structure of the complex formed. Complexation twists both oxalyl arms by 180掳, strengthens the intramolecular (amide)CO路路路H(Csp<sup>2sup>)路路路OC(amide) three-centered hydrogen bond, and moves apart the oxalyl arms to allow the accommodation of the 1,3-benzenediol inside the cavity. The supramolecular architectures of the complexes in 1-D are directed by R<sup>1sup><sub>2sub>(6), R<sup>2sup><sub>2sub>(10), and R<sup>1sup><sub>2sub>(6) adjacent hydrogen-bonding ring motifs; meanwhile, the 2-D and 3-D arrays are driven by multipolar interactions. Theoretical DFT calculations at the B3LYP/6-31G(d,p) level of theory were performed to support the experimental findings. The complexes herein reported constitute the first examples of molecular complexes with phenyldioxalamate.