Hexane-1,2,5,6-tetrol as a Versatile and Biobased Building Block for the Synthesis of Sustainable (Chiral) Crystalline Mesoporous Polyboronates.

Autor:	De Bruyn M; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States.; Faculty of Science, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., Cuello-Penaloza P; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Cendejas M; Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States., Hermans I; Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States., He J; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Krishna SH; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Lynn DM; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Dumesic JA; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Huber GW; Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States., Weckhuysen BM; Faculty of Science, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Jazyk:	angličtina
Zdroj:	ACS sustainable chemistry & engineering [ACS Sustain Chem Eng] 2019 Aug 05; Vol. 7 (15), pp. 13430-13436. Date of Electronic Publication: 2019 Jul 03.
DOI:	10.1021/acssuschemeng.9b02772
Abstrakt:	We report on the synthesis and characterization of novel mesoporous chiral polyboronates obtained by condensation of ( R , S )/( S , S )-hexane-1,2,5,6-tetrol (HT) with simple aromatic diboronic acids (e.g., 1,3-benzenediboronic acid) (BDB). HT is a cellulose-derived building block comprising two 1,2-diol structures linked by a flexible ethane bridge. It typically consists of two diastereomers one of which [( S , R )-HT] can be made chirally pure. Boronic acids are abundantly available due to their importance in Suzuki-Miyaura coupling reactions. They are generally considered nontoxic and easy to synthesize. Reactive dissolution of generally sparingly soluble HT with BDB, in only a small amount of solvent, yields the mesoporous HT/polyboronate materials by spontaneous precipitation from the reaction mixture. The 3D nature of HT/polyboronate materials results from the entanglement of individual 1D polymeric chains. The obtained BET surface areas (SAs) and pore volumes (PVs) depend strongly on HT's diastereomeric excess and the meta/para orientation of the boronic acids on the phenyl ring. This suggests a strong influence of the curvature(s) of the 1D polymeric chains on the final materials' properties. Maximum SA and PV values are respectively 90 m 2 g -1 and 0.44 mL g -1 . Variably sized mesopores, spanning mainly the 5-50 nm range, are evidenced. The obtained pore volumes rival the ones of some covalent organic frameworks (COFs), yet they are obtained in a less expensive and more benign fashion. Moreover, currently no COFs have been reported with pore diameters in excess of 5 nm. In addition, chiral boron-based COFs have presently not been reported. Scanning electron microscopy reveals the presence of micrometer-sized particles, consisting of aggregates of plates, forming channels and cell-like structures. X-ray diffraction shows the crystalline nature of the material, which depends on the nature of the aromatic diboronic acids and, in the specific case of 1,4-benzenediboronic acid, also on the applied diastereomeric excess in HT. Competing Interests: The authors declare no competing financial interest. (Copyright © 2019 American Chemical Society.)
Databáze:	MEDLINE
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