Supplemental data
Synthesis, characterization, photoluminescent properties and supramolecular aggregations in
diimine chelated cadmium dihalides
TUSHAR S. BASU BAUL*, SAJAL KUNDU, SEIK WENG NG, NIKHIL GUCHHAIT and
EDWARD R. T. TIEKINK*
Figure S1. UV-Vis spectra of 1-12 in acetonitrile (concentration ~10-5 M). Spectra of 4, 5, 10 and 11,
with -OMe substituents, are shown separately for convenience.
1
2
3
6
7
8
9
12
1.0
Absorbence
Absorbence
1.0
0.5
0.5
0.0
0.0
300
4
5
10
11
350
400
450
300
350
400
Wavelength (nm)
Wavelength (nm)
1
450
Figure S2. Fluorescence spectra of 1-12 in acetonitrile (concentration ~10-5 M) obtained by excitation
at the respective absorption maxima. Spectra of 4, 5, 10 and 11, with -OMe substituents are shown
separately for convenience.
400
450
500
550
4
5
10
11
Fluorescence intensity (arb. unit)
Fluorescence intensity (arb. unit)
1
2
3
6
7
8
9
12
400
600
450
500
550
600
Wavelength (nm)
Wavelength (nm)
Figure S3. Solid state fluorescence spectra of 1-12 obtained by excitation at the respective absorption
maxima. Spectra of 4, 5, 10 and 11, with -OMe substituents, are shown separately for convenience.
400
450
500
550
600
650
Wavelength (nm)
4
5
10
11
Fluorescence intensity (arb. unit)
Fluorescence intensity (arb. unit)
1
2
3
6
7
8
9
12
400
450
500
550
Wavelength (nm)
2
600
650
Figure S4. Molecular structures of (a) binuclear [Cd(Br)2(L2)]2·C6H6 (2) {unlabelled atoms are related
by the symmetry operation 1-x, 1-y, 1-z; the solvent molecule is omitted}. (b) binuclear [Cd(Br)2(L3)]2
(3) {symmetry operation 1-x, 1-y, 1-z}. (c) binuclear [Cd(Br)2(L5)]2·2CH3CN (5) {symmetry
operation 1-x, 1-y, 1-z; the solvent molecules are omitted}. (d) binuclear [Cd(Cl)2(L6)]2 (7) {symmetry
operation 1-x, 1-y, 1-z}. (e) binuclear [Cd(I)2(L3)]2 (8) {symmetry operation 1-x, 1-y, 1-z}. (f)
binuclear [Cd(I)2(L6)]2 (12) {symmetry operations 1-x, 1-y, 1-z}. (g) mononuclear [Cd(I)2(L4)] (10).
(a)
(b)
3
Figure 4 (continued)
(c)
(d)
4
Figure 4 (continued)
(e)
(f)
5
Figure 4 (continued)
(g)
6
Figure S5. Unit cell contents for 1 viewed in projection down the b-axis highlighting the stacking of
supramolecular layers along the c-axis. The ... interactions are indicated as purple dashed lines.
7
Figure S6. Unit cell contents for 8 viewed in projection down the b-axis highlighting the stacking of
supramolecular layers along the c-axis. The ... interactions are indicated as purple dashed lines.
Geometric parameters: (Cd,N1,N2,C5,C6) and (N1,C1-C5)i rings, inter-centroid distance =
3.794(3) Å, angle of inclination between the rings = 5.8(2)° for symmetry operation i: 1-x, 2-y, 1-z.
(N1,C1-C5) and (C7-C12)ii rings, inter-centroid distance = 3.941(3) Å, angle of inclination = 11.0(3)°
for symmetry operation ii: -x, 2-y, 1-z.
8
Figure S7. Unit cell contents for 3 viewed in projection down the a-axis. The C–H...Br [C3H3...Br1i
= 2.90 Å, C3...Br1i = 3.665(3) Å and angle at H3 = 138° for symmetry operation i: ½+x, 1½-y, -½+z.
C6–H6...Br2ii = 2.89 Å, C6...Br2ii = 3.752(3) Å and angle at H3 = 151° for symmetry operation ii:
½-x, ½+y, ½-z] and ... [(N1,C1-C5) and (C7-C12)iii rings, inter-centroid distance = 3.6593(19) Å,
angle of inclination between the rings = 8.62(17)° for symmetry operation iii: 1+x, y, z]. (N1,C1-C5)
and (C7-C12)i rings, inter-centroid distance = 3.806(2) Å, angle of inclination = 18.97(17)°]
interactions are indicated as orange and purple dashed lines, respectively.
9
Figure S8. Unit cell contents for 7 viewed in projection down the a-axis. The C–H...Cl and ...
interactions are indicated as orange and purple dashed lines, respectively. Geometric parameters:
C3H3...Cl1i = 2.80 Å, C3...Cl1i = 3.515(6) Å and angle at H3 = 133° for symmetry operation i: ½+x, 1½-y, ½+z. C6–H6...Cl2ii = 2.71 Å, C6...Cl2ii = 3.587(6) Å and angle at H3 = 153° for
symmetry operation ii: 1½-x, ½+y, 1½-z. (N1,C1-C5) and (C7-C12)iii rings, inter-centroid distance =
3.903(4) Å, angle of inclination between the rings = 18.1(3)° for symmetry operation iii: -1+x, y, z.
(N1,C1-C5) and (C7-C12)i rings, inter-centroid distance = 3.885(4) Å, angle of inclination = 20.8(3)°.
10
Figure S9. Unit cell contents for 12 viewed in projection down the a-axis. The C–H...I, C-H...Cl, and
... interactions are indicated as orange, blue and purple dashed lines, respectively. Geometric
parameters: C3–H3...I1i = 3.17 Å, C3...I1i = 4.023(3) Å and angle at H3 = 121° for symmetry
operation i: ½+x, ½-y, -½+z. C6–H6...I2ii = 3.16 Å, C6...I2ii = 4.023(3) Å and angle at H6 = 156° for
symmetry operation ii: ½-x, -½+y, ½-z. C3–H3...Cl1ii = 2.79 Å, C6...Cl1ii = 3.488(3) Å and angle at
H3 = 131°. (N1,C1-C5) and (C7-C12)iii rings, inter-centroid distance = 3.5839(17) Å, angle of
inclination between the rings = 3.29(14)° for symmetry operation iii: 1+x, y, z. (N1,C1-C5) and
(C7-C12)i rings, inter-centroid distance = 3.8661(16) Å, angle of inclination = 16.69(14)°.
11
Figure S10. Unit cell contents for 4 viewed in projection down the a-axis. The C–H...Br and ...
interactions indicated as orange and purple dashed lines, respectively.
12
Figure S11. Unit cell contents for 10 viewed in projection down the a-axis. The C–H...I and ...
interactions indicated as orange and purple dashed lines, respectively. Geometric parameters:
C6H6...I1i = 3.11 Å, C6...I1i = 4.029(6) Å and angle at H6 = 164° for symmetry operation i: 1+x, y,
-1+z. C1–H1...I2i = 3.10 Å, C1...I2i = 3.944(7) Å and angle at H6 = 148° for symmetry operation i:
x, 1-y, -½+z. (C7-C12) and (C7-C12)iii rings, inter-centroid distance = 4.356(5) Å, angle of inclination
between the rings = 15.3(3)° for symmetry operation iii: x, 2-y, -½+z.
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Figure S12. (a) A view of the supramolecular array in the ab-plane for 6 sustained by CH...Cl
[C4H4...Cl2i = 2.63 Å, C6...Cl1i = 3.375(3) Å and angle at H4 = 135° for symmetry operation i:
x, 1+y, z] and ∙∙∙ [(C7-C12) and (C7-C12)ii rings the inter-centroid distance = 3.6280(15) Å, the
angle of inclination between the rings = 0° for symmetry operation ii: 1-x, 2-y, 1-z] interactions,
indicated as orange and purple dashed lines, respectively. (b) Unit cell contents for 6 viewed in
projection down the a-axis and highlighting the stacking of supramolecular layers along the c-axis.
The C–H...Cl and ... interactions are indicated as orange and purple dashed lines, respectively.
(a)
(b)
14
Figure S13. Unit cell contents for 9 viewed in projection down the a-axis and highlighting the
stacking of supramolecular layers along the a-axis. The C–H... and ... interactions are indicated as
brown and purple dashed lines, respectively.
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Figure S14. (a) A view of the supramolecular array in the ac-plane for 11 sustained by C–H...O
[C2H2...O1i = 2.42 Å, C2...O1i = 3.255(5) Å and angle at H2 = 147° for symmetry operation i: 1+x,
1-y, -½+z] and ∙∙∙ [(N1,C1-C5) and (C7-C12)ii rings the inter-centroid distance = 3.639(2) Å, the
angle of inclination between the rings = 5.36(17)° for symmetry operation ii: 1-x, 1-y, 1-z]
interactions, indicated as orange and purple dashed lines, respectively. (b) Unit cell contents for 11
viewed in projection down the a-axis highlighting the stacking of supramolecular layers along the
b-axis. The C–H...O and ... interactions are indicated as orange and purple dashed lines,
respectively.
(a)
(b)
16