期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 72, 页码 17588-17597出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202003909
关键词
cyclophanes; hydrogen bonds; polymers; self-assembly; supramolecular chemistry
资金
- American Chemical Society Petroleum Research Fund [56665-ND4]
- National Science Foundation [CHE-1904534]
- NSF [CHE-1828064]
- University of Florida [CHE-1828064]
- National Institutes of Health [NIH S10 OD021758-01A1]
- UF Center for Nuclear Magnetic Resonance Spectroscopy
Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ([n.n]pCps, n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ([n.n]pCps) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a approximate to 30-fold increase in the elongation constant for the [2.2]pCp-4,7,12,15-tetraanilide ([2.2]pCpNTA) compared to previously reported [2.2]pCp-4,7,12,15-tetracarboxamide ([2.2]pCpTA), and a approximate to 300-fold increase in the elongation constant for the [3.3]pCp-5,8,14,17-tetraanilide ([3.3]pCpNTA) compared to previously reported [3.3]pCp-5,8,14,17-tetracarboxamide ([3.3]pCpTA). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers-revealed by computations and X-ray crystallography-resulting in a more favorable slipped stacking of the intermolecular pi-surfaces ([n.n]pCpNTA vs. [n.n]pCpTA), and a more complementary H-bonding geometry ([3.3]pCpNTA vs. [2.2]pCpNTA).
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