TY - JOUR
T1 - A 1-hydroxy-2,3,1-benzodiazaborine-containing π-conjugated system
T2 - synthesis, optical properties and solvent-dependent response toward anions
AU - Satta, Yusuke
AU - Nishiyabu, Ryuhei
AU - James, Tony D.
AU - Kubo, Yuji
PY - 2017/4/13
Y1 - 2017/4/13
N2 - Our interest in the functionalization of [sbnd]OH-substituted azaborines prompted us to synthesize a 1-hydroxy-2,3,1-benzodiazaborine conjugated with 1,8-naphthalimide 1. Its fluorescence was dramatically affected by the nature of the solvent. In particular, the use of DMSO, which has a relatively high donor number (DN = 29.8), led to a remarkable decrease in the fluorescence intensity (ΦF = 0.0014), possibly due to intermolecular hydrogen-bonding interactions (Me2S[dbnd]O⋯HO[sbnd]B). The presence of the hydroxyl group on boron led to a solvent-driven colorimetric response towards anions; high selectivity for F− over other anions in DMSO, and responded to AcO− and F− in THF, as shown by UV/vis titrations, NMR, and mass spectroscopic analysis. The nucleus-independent chemical shift (NICS) indices suggested that hydrogen bonding interactions between Me2S[dbnd]O and HO[sbnd]B reduced the aromaticity of the benzodiazaborine macrocycle, causing an increase in the negative character of the boron. The increase in the polarity of the B[sbnd]N bond may prevent acetate-binding of 1 in DMSO.
AB - Our interest in the functionalization of [sbnd]OH-substituted azaborines prompted us to synthesize a 1-hydroxy-2,3,1-benzodiazaborine conjugated with 1,8-naphthalimide 1. Its fluorescence was dramatically affected by the nature of the solvent. In particular, the use of DMSO, which has a relatively high donor number (DN = 29.8), led to a remarkable decrease in the fluorescence intensity (ΦF = 0.0014), possibly due to intermolecular hydrogen-bonding interactions (Me2S[dbnd]O⋯HO[sbnd]B). The presence of the hydroxyl group on boron led to a solvent-driven colorimetric response towards anions; high selectivity for F− over other anions in DMSO, and responded to AcO− and F− in THF, as shown by UV/vis titrations, NMR, and mass spectroscopic analysis. The nucleus-independent chemical shift (NICS) indices suggested that hydrogen bonding interactions between Me2S[dbnd]O and HO[sbnd]B reduced the aromaticity of the benzodiazaborine macrocycle, causing an increase in the negative character of the boron. The increase in the polarity of the B[sbnd]N bond may prevent acetate-binding of 1 in DMSO.
KW - 1,8-Naphthalimide
KW - 2,3,1-Benzodiazaborine
KW - Anion sensing
KW - Azaborine
KW - Photophysical studies
UR - http://www.scopus.com/inward/record.url?scp=85014388942&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1016/j.tet.2017.02.050
U2 - 10.1016/j.tet.2017.02.050
DO - 10.1016/j.tet.2017.02.050
M3 - Article
AN - SCOPUS:85014388942
SN - 0040-4020
VL - 73
SP - 2053
EP - 2061
JO - Tetrahedron
JF - Tetrahedron
IS - 15
ER -