Supplementary material
Fluorescent sensors based on BODIPY derivatives for aluminium ion recognition: an experimental and theoretical study
Tasawan Keawwangchai · Nongnit Morakot · Banchob Wanno
T. Keawwangchai · N. Morakot () · B. Wanno ()
The Center of Excellence for Innovation in Chemistry (PERCH−CIC) and Supramolecular Chemistry Research Unit, Department of Chemistry, Faculty of Science, Mahasarakham University, Maha Sarakham, 44150, Thailand
Phone/fax: +66 4375 4246, e−mail: (N. Morakot), (B. Wanno)
Table S1 Selected geometrical data for sensor L1 and its metal ion complexes computed at the B3LYP/LANL2DZ level of theory
Parameter a / L1 / L1/Na+ / L1/Ag+ / L1/Ca2+ / L1/Co2+ / L1/Ni+ / L1/Cu2+ / L1/Zn2+ / L1/Al3+Distances (Ǻ)
C3-C4 / 1.408 / 1.403 / 1.400 / 1.402 / 1.400 / 1.402 / 1.400 / 1.401 / 1.403
C4-O1 / 1.399 / 1.453 / 1.443 / 1.470 / 1.463 / 1.449 / 1.460 / 1.452 / 1.458
C4-C5 / 1.409 / 1.403 / 1.401 / 1.401 / 1.400 / 1.402 / 1.400 / 1.402 / 1.403
O1-M / - / 2.216 / 2.263 / 2.337 / 1.964 / 1.899 / 1.948 / 2.134 / 2.199
O1-H1 / 0.979 / 0.979 / 0.979 / 0.982 / 0.981 / 0.980 / 0.981 / 0.984 / 0.987
N1-B / 1.534 / 1.538 / 1.539 / 1.544 / 1.541 / 1.548 / 1.547 / 1.548 / 1.559
N2-B / 1.534 / 1.538 / 1.539 / 1.545 / 1.540 / 1.548 / 1.547 / 1.548 / 1.558
B-F1 / 1.449 / 1.443 / 1.440 / 1.431 / 1.429 / 1.425 / 1.426 / 1.424 / 1.412
B-F2 / 1.449 / 1.443 / 1.441 / 1.431 / 1.429 / 1.425 / 1.426 / 1.425 / 1.412
Angles (°)
H1-O1-C4 / 112.4 / 111.8 / 112.8 / 110.6 / 112.1 / 114.5 / 112.5 / 112.8 / 111.5
M-O1-H1 / - / 135.9 / 123.2 / 131.8 / 121.4 / 121.5 / 120.5 / 119.8 / 117.1
M-O1-C4 / - / 112.3 / 123.3 / 117.7 / 126.6 / 124.0 / 127.0 / 127.4 / 131.5
O1-C4-C3 / 116.8 / 118.9 / 117.6 / 118.4 / 118.6 / 118.4 / 118.6 / 118.6 / 118.9
O1-C4-C5 / 122.9 / 118.9 / 120.1 / 118.9 / 118.6 / 118.9 / 118.6 / 118.9 / 118.9
C2-C1-C7 / 120.6 / 120.4 / 120.3 / 120.2 / 120.6 / 121.0 / 120.2 / 119.6 / 120.2
C6-C1-C7 / 120.6 / 120.4 / 120.5 / 120.4 / 120.6 / 119.4 / 120.2 / 120.7 / 120.2
C1-C7-C8 / 119.7 / 119.5 / 119.5 / 119.8 / 121.6 / 120.2 / 120.2 / 120.4 / 121.2
C1-C7-C15 / 119.7 / 119.2 / 119.6 / 119.8 / 121.8 / 120.3 / 120.3 / 120.4 / 121.5
N1-B-N2 / 108.3 / 108.1 / 107.9 / 107.2 / 106.1 / 106.6 / 106.7 / 106.5 / 105.2
N1-B-F1 / 110.3 / 110.2 / 110.1 / 110.0 / 110.2 / 109.9 / 109.9 / 110.0 / 109.7
N2-B-F1 / 110.3 / 110.1 / 110.1 / 109.9 / 110.3 / 109.9 / 109.9 / 109.9 / 109.8
N2-B-F2 / 110.3 / 110.1 / 110.1 / 109.9 / 110.3 / 109.9 / 109.9 / 109.9 / 109.8
F1-B-F2 / 107.3 / 108.2 / 108.5 / 109.8 / 109.8 / 110.5 / 110.4 / 110.6 / 112.3
Dihedral angles (°)
H1-O1-C4-C3 / 180.0 / 91.4 / 143.1 / 97.6 / 90.0 / 96.4 / 90.1 / 96.8 / 90.5
H1-O1-C4-C5 / 0.0 / -91.2 / -38.2 / -82.2 / -89.7 / -83.7 / -89.6 / -84.6 / -89.4
M-O1-C4-C3 / - / -88.6 / -45.9 / -82.4 / -90.0 / -85.7 / -90.0 / -84.7 / -89.5
M-O1-C4-C5 / - / 88.8 / 132.7 / 97.8 / 90.3 / 94.2 / 90.3 / 93.9 / 90.5
C2-C1-C7-C8 / -90.0 / -90.0 / -90.6 / -89.8 / -89.9 / -90.8 / -89.8 / -91.9 / -89.7
C2-C1-C7-C15 / 90.0 / 90.0 / 88.9 / 90.2 / 90.1 / 92.6 / 90.2 / 85.9 / 90.3
C6-C1-C7-C8 / 90.0 / 90.1 / 89.0 / 89.3 / 89.7 / 88.9 / 89.8 / 88.1 / 89.8
C6-C1-C7-C15 / -90.0 / -89.9 / -91.5 / -90.7 / -90.4 / -87.7 / -90.2 / -94.1 / -90.2
a Atomic labels are defined in Fig. 3
Table S2 Selected geometrical data for sensor L2 and its metal ion complexes computed at the B3LYP/LANL2DZ level of theory
Parameter a / L2 / L2/Na+ / L2/Ag+ / L2/Ca2+ / L2/Co2+ / L2/Ni2+ / L2/Cu2+ / L2/Zn2+ / L2/Al3+Distances (Ǻ)
C3-O2 / 1.394 / 1.400 / 1.424 / 1.419 / 1.419 / 1.423 / 1.399 / 1.429 / 1.414
C4-O1 / 1.394 / 1.424 / 1.423 / 1.416 / 1.416 / 1.422 / 1.417 / 1.427 / 1.413
O1-M / - / 2.273 / 2.316 / 2.359 / 2.069 / 1.982 / 2.061 / 2.119 / 2.269
O2-M / - / 2.274 / 2.322 / 2.362 / 2.071 / 1.986 / 2.060 / 2.130 / 2.306
O1-H1 / 0.979 / 0.978 / 0.978 / 0.979 / 0.979 / 0.979 / 0.979 / 0.981 / 0.984
O2-H2 / 0.980 / 0.978 / 0.978 / 0.978 / 0.978 / 0.979 / 0.979 / 0.981 / 0.983
N1-B / 1.534 / 1.538 / 1.538 / 1.548 / 1.548 / 1.547 / 1.548 / 1.546 / 1.559
N2-B / 1.534 / 1.538 / 1.538 / 1.548 / 1.548 / 1.547 / 1.548 / 1.548 / 1.559
B-F1 / 1.449 / 1.441 / 1.441 / 1.425 / 1.425 / 1.425 / 1.425 / 1.426 / 1.411
B-F2 / 1.449 / 1.445 / 1.444 / 1.427 / 1.427 / 1.428 / 1.427 / 1.428 / 1.412
Angles (°)
H1-O1-C4 / 111.8 / 111.1 / 112.9 / 114.6 / 114.6 / 115.6 / 114.7 / 114.8 / 115.1
H2-O2-C3 / 111.9 / 111.2 / 112.9 / 114.9 / 114.9 / 115.9 / 114.9 / 115.1 / 116.0
M-O1-H1 / - / 133.0 / 130.7 / 130.6 / 130.6 / 131.0 / 131.6 / 128.1 / 122.4
M-O1-C4 / - / 115.9 / 116.4 / 114.8 / 130.4 / 113.4 / 113.7 / 117.1 / 122.5
M-O2-H2 / - / 132.9 / 130.8 / 130.4 / 114.8 / 130.8 / 131.3 / 128.1 / 122.7
M-O2-C3 / - / 115.9 / 116.3 / 114.7 / 114.7 / 113.3 / 113.8 / 116.8 / 121.3
O1-M-O2 / - / 73.4 / 72.0 / 79.1 / 79.1 / 82.7 / 80.3 / 75.9 / 68.0
O1-C4-C3 / 117.3 / 117.5 / 117.7 / 115.9 / 115.9 / 115.4 / 116.3 / 115.2 / 114.4
O1-C4-C5 / 123.4 / 122.6 / 122.2 / 123.8 / 123.8 / 124.0 / 123.5 / 124.1 / 125.0
O2-C3-C2 / 123.1 / 122.2 / 121.9 / 123.6 / 123.6 / 123.7 / 123.3 / 124.0 / 125.2
O2-C3-C4 / 117.2 / 117.4 / 117.6 / 115.6 / 115.6 / 115.2 / 116.0 / 115.0 / 113.8
C2-C1-C7 / 119.8 / 119.6 / 120.1 / 120.1 / 120.1 / 119.7 / 120.2 / 119.9 / 120.2
C6-C1-C7 / 121.1 / 121.3 / 120.8 / 120.4 / 120.4 / 120.6 / 120.5 / 120.4 / 119.9
C1-C7-C8 / 119.7 / 119.3 / 119.3 / 120.2 / 120.2 / 120.1 / 120.2 / 120.1 / 121.3
C1-C7-C15 / 119.7 / 119.3 / 119.3 / 120.2 / 120.2 / 120.1 / 120.2 / 120.0 / 121.3
N1-B-N2 / 108.3 / 108.1 / 108.1 / 106.7 / 106.7 / 106.7 / 106.7 / 106.8 / 105.1
N1-B-F1 / 110.3 / 110.2 / 110.2 / 110.0 / 110.0 / 110.0 / 110.0 / 110.1 / 109.8
N1-B-F2 / 110.3 / 110.0 / 110.0 / 109.9 / 109.9 / 109.9 / 109.9 / 110.0 / 109.7
N2-B-F1 / 110.3 / 110.2 / 110.2 / 110.0 / 110.0 / 110.0 / 110.0 / 109.9 / 109.8
N2-B-F2 / 110.3 / 110.0 / 110.0 / 109.9 / 109.9 / 109.8 / 109.9 / 109.7 / 109.7
F1-B-F2 / 107.3 / 108.2 / 108.3 / 110.5 / 110.5 / 110.3 / 110.5 / 110.3 / 112.4
Dihedral angles (°)
H1-O1-C4-C3 / 179.9 / -180.0 / -179.4 / -179.9 / -179.9 / 179.6 / 180.0 / -179.6 / 180.0
H1-O1-C4-C5 / -0.1 / 0.0 / 0.7 / 0.1 / 0.1 / -0.4 / 0.0 / 0.3 / 0.0
H2-O2-C3-C2 / 0.1 / 0.0 / -0.7 / -0.1 / -0.1 / -0.7 / 0.0 / -1.0 / 0.0
H2-O2-C3-C4 / -180.0 / 180.0 / -179.3 / 179.9 / 179.9 / 179.4 / -180.0 / 179.0 / 180.0
H1-O1-M-O2 / - / 180.0 / 179.5 / 179.9 / 179.9 / -179.3 / -180.0 / 179.7 / -180.0
H2-O1-M-O1 / - / -180.0 / -179.3 / -179.9 / -179.9 / -179.1 / 180.0 / -178.7 / -180.0
M-O1-C4-C3 / - / 0.0 / 1.1 / 0.0 / 0.0 / -0.5 / 0.0 / 0.5 / 0.0
M-O1-C4-C5 / - / -180.0 / -178.8 / -180.0 / -180.0 / 179.5 / 180.0 / -179.6 / -180.0
M-O2-C3-C2 / - / 180.0 / 179.0 / 180.0 / 180.0 / -179.2 / 0.0 / 179.9 / 180.0
M-O2-C3-C4 / - / 0.0 / -0.9 / 0.0 / 0.0 / 0.9 / 0.0 / -0.1 / 0.0
C2-C1-C7-C8 / -89.7 / -89.5 / -88.9 / -90.2 / -90.2 / -90.0 / -90.1 / -85.5 / -90.6
C2-C1-C7-C15 / 89.6 / 89.5 / 91.3 / 90.2 / 90.2 / 89.8 / 90.1 / 94.8 / 90.7
C6-C1-C7-C8 / 90.3 / 90.5 / 91.1 / 89.8 / 89.8 / 89.8 / 89.9 / 94.0 / 89.4
C6-C1-C7-C15 / -90.4 / -90.5 / -88.8 / -89.8 / -89.8 / -90.4 / -89.9 / -85.6 / -89.3
a Atomic labels are defined in Fig. 3
Table S3 The computed orbital energies (ELUMO or EHOMO) and frontier molecular orbital energy gap (DEHOMO-LUMO) of the sensors L1, L2 and their complexes with metal ions computed at B3LYP/LanL2DZ level of theory.
Metal ion / L1 / L2ELUMOa / EHOMOa / DEHOMO-LUMOa / ELUMOa / EHOMOa / DEHOMO-LUMOa
None / -0.100 / -0.210 / 0.110 / -0.102 / -0.211 / 0.109
Na+ / -0.179 / -0.283 / 0.104 / -0.178 / -0.284 / 0.106
Ag+ / -0.284 / -0.296 / 0.012 / -0.272 / -0.287 / 0.015
Ca2+ / -0.383 / -0.395 / 0.012 / -0.373 / -0.385 / 0.012
Co2+ / -0.394 / -0.474b / 0.080c / -0.332 / -0.436b / 0.094c
Ni2+ / -0.421 / -0.434 / 0.013 / -0.415 / -0.427 / 0.012
Cu2+ / -0.362 / -0.454b / 0.092c / -0.388 / -0.482b / 0.104c
Zn2+ / -0.425 / -0.438 / 0.013 / -0.414 / -0.426 / 0.012
Al3+ / -0.550 / -0.604 / 0.054 / -0.554 / -0.569 / 0.015
a In eV.
b ESOMO.
c DESOMO-LUMO.
Fig. S1 Mass spectrum of L1.
Fig. S2 1H-NMR spectrum of L1 in CDCl3 with 400 MHz.
Fig. S3 13C-NMR spectrum of L1 in DMSO-d6 with 400 MHz.
Fig. S4 Mass spectrum of L2.
Fig. S5 1H-NMR spectrum of L2 in CDCl3 with 400 MHz.
Fig. S6 13C-NMR spectrum of L2 in DMSO-d6 with 400 MHz.