Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
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Conflicts of interest
The authors declare no conflicts of interests.
DOI: 10.1039/C9NJ01772K
Acknowledgements
This work was supported by JSPS KAKENHI Grant Numbers
JP17H03062, JP18H04495, JP15K17861.
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Notes and references
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2
Figure 5. Plots of observed association constant (K
a
) (derived using Arrhenius–Ostwald
5
·1, and TBA·TFPB, vs dielectric constant (ε). The
of an electrolyte with a specific sum of ionic radii (0.5, 0.6,
equation) of (TPP)
lines represent calculated K
.9, and 1.3 nm) vs dielectric constant (ε) derived using Bjerrum’s theory.
5
·1, TPP·TFPB, (TBA)
a
0
6
7
a
The uniform decrease of K for the conventional organic
electrolytes TPP·TFPB and TBA·TFPB with increase of ε
consistent with the prediction derived from Bjerrum’s theory.
a
The observed K for TPP·TFPB and TBA·TFPB well agreed with
the theoretical curve for electrolytes with 1.3 nm and 0.9 nm,
the sum of the ionic radii which are roughly estimated by
molecular modelling, respectively, as shown in Figure 5. On
another front, K
were not consistent with the theoretical curves. For an
8
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1
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s for the borate pentads (TPP) ·1 and (TBA) ·1
1
4
-1
example, K
clearly higher than the predicted K
a
for (TPP)
5
·1 in dichloromethane (6.4×10 L·mol ) is
curve which is consistent
1
485–1488.
a
4
-
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1
). This mismatch comes from the assumption of the
1
4 B. A. Blight, C. A. Hunter, D. A. Leigh, H. McNab and P. I. T.
monovalent electrolytes for Arrhenius–Ostwald equation. In
other words, multivalent ionic dissociation of the borate 15 S. Lin, M. A. Ischay, C. G. Fry and T. P. Yoon, J. Am. Chem. Soc.,
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1
6 K. Nishi, S. Tochioka, T. Hiroi, T. Yamada, K. Kokado, T.-H. Kim,
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Conclusions
19 T. Yamada, K. Kokado, Y. Higaki, A. Takahara and K. Sada,
As a summary of this study, we synthesized tetrahedral borate
pentads by using a typical azide alkyne click reaction. The 20 Y. Furukawa, K. Kokado and K. Sada, Chem. Lett., 2012, 41, 667
obtained borate pentads exhibited a rapid exchange of counter
cations, revealed by NMR spectroscopies. From the
conductometry, the borate pentads behaved as a typical weak
electrolyte, thus the molar conductivity rapidly increased at
Chem. Lett., 2014, 43, 1300−1302.
−668.
2
1 M. Ohta, T. Ono, K. Kokado, A. Kakugo and K. Sada, Macromol.
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around the limit of dilution, which was similar with that for the 23 T. Yamada, K. Kokado and K. Sada, Langmuir, 2017, 33, 2610–
2
616.
reference organic electrolytes. However, the association
constants for the obtained borate pentads were not consistent
with those predicted by using Bjerrum’s theory, probably due to
the variation of valence with the change of dielectric constant
of the media.
2
4 N. Bjerrum, Det Kgl. Danske Videnskab. Selskab Math.-fys.
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