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note
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These angles were calculated from the optimized structure by molecular mechanics calculations (MMFF) using Spartan. In the calculations, long alkyl chains were replaced by methyl groups.
-
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33
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84935885874
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note
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Diboronic acids are known to exist as mixtures of acid and anhydride forms in the solid state. Also see ref 1c.
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34
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84935849027
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note
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Similar upfield shifts of the 11B NMR signals were observed for 6-mer and 12-mer, where the phenylboroxine moieties are not planar in the modeling study. Ligation to boron by a base such as water was not clearly observed in the NMR spectrum.
-
-
-
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36
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84935850149
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note
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The volumes of 6-mer and 12-mer were estimated from the inside octahedron with an edge length of 16.0 Å or cuboctahedron with an edge length of 12.3 Å, respectively. For a size comparison of the largest class of covalent organic cages, see the Supporting Information.
-
-
-
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37
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84935869004
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note
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Diboronic acids S1 and S2 have a bond angle of ca. 120 between the two C-B bonds but different dihedral angles between the boronic acid-bound phenyl ring and the central benzene ring. While S1 did not give any discrete boroxine, S2, which has a larger dihedral angle, gave a discrete boroxine partially. See the Supporting Information for details.
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47
-
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84935878345
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note
-
3-mer, 6-mer, and 12-mer, which have the same alkyl chains (R = C14H29), were used for the comparison of the relative sizes. 6-mer (R = C14H29) was prepared in the same manner as 6-mer (R = C6H13), whose structure was determined by single-crystal X-ray diffraction. See the Supporting Information for details.
-
-
-
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48
-
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84935844893
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note
-
It is not clear whether a boroxine or a window faces the Au surface. However, because of the high symmetry of the boroxine cages, the height profiles among boroxine cages could be compared.
-
-
-
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49
-
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84935872346
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note
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The apparent lateral sizes extracted from the STM images are overestimated because of the tip convolution effect, in which the tip shape is convoluted into the STM images.(25) On the other hand, the reduced apparent height of the boroxine cages with respect to the physical height can be ascribed to tip-induced deformation for the series of boroxine-based architectures during STM imaging. For further details, see the Supporting Information.
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50
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