Chapter 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly
4.5. Summary …
To rationalize the influence of the non- covalent interactions of anion on the formation of supramolecular architectures with aryl-azo diazonium salts, we have shown that the size of the anions has marked influence upon the supramolecular assemblies. For the complexes with the different type of anions (linear, planner, spherical), one dimensional layered network with identical topologies has been found. As expected, the N atom of imidazole ring always acts as an excellent hydrogen-bonding acceptor by the formation of a strong O-Η····Ν or ionic N-H···· O and O-Η····Ο hydrogen bond due to the presence of water in the crystal systems. Additionally, this study shows that complex 1 and 5 is a good supramolecular building module that can produce bimolecular co crystals, and its modular nature makes it possible to select a comfortable configuration in the course of formation of self assembly hydrogen bond (L····LH+). Finally UV-Visible and fluorescence spectroscopy studies also confirmed the existence of weak supramolecular interaction.
These results show that the types and ratios of cations and anions play significant roles in fabricating different solid-state structure.
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Chapter - 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly
APPENDIX
Table 4.1 A. Crystal Data and Structure Refinement for salt 1, 2, 3, 4 and 5.
Salt 1 Salt 2 Salt 3 Salt 4 Salt 5
CCDC No 736670 736671 736672 736673 736674
Empirical formula C19H17N9OSBr2 C9H10N5O4I C9 H10 N4O5ClI C13H11N5O3 C26H23N9O4
Fw 579.30 379.12 416.56 285.27 525.53
crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
space group P2(1)/c P2(1)/n P2(1)/n P2(1)/c P2(1)
a, Å 12.1694(3) 4.88350(10) 5.60440(10) 6.8263(2) 5.6061(2)
b, Å 13.9841(4) 10.1720(3) 8.8412(2) 11.5549(3) 15.8135(6)
c, Å 14.3235(4) 27.4296(8) 29.3023(6) 17.0562(4) 14.0347(5)
α, deg 90 90 90 90 90
β, deg 105.557(2) 91.328(2) 95.3470(10) 96.7880(10) 97.281(2)
γ, deg 90 90 90 90 90
V, Å3 2348.24(11) 1362.20(6) 1445.60(5) 1335.92(6) 1234.17(8)
Z 4 4 4 4 2
µ 3.572 2.372 2.426 0.107 0.102
F(000) 1152 764 1101 700 572
GOF(S) 1.055 1.050 1.028 1.004 0.973
Rint 0.0379 0.0402 0.0213 0.0251 0.0521
final R indices R1=0.0452 R1= 0.0343 R1= 0.0356 R1= 0.0473 R1= 0.0519 [I > 2σ(I)] wR2= 0.0918 wR2= 0.0675 wR2= 0.0963 wR2= 0.1172 wR2= 0.1135 R indices (all data) R1= 0.0839 R1= 0.0752 R1= 0.0485 R1= 0.0898 R1= 0.0830
wR2= 0.1100 wR2= 0.0495 wR2= 0.1054 wR2= 0.1473 wR2= 0.1445
Chapter - 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly Table 4.2 A. Selected Non-covalent interactions in salt 1-5
D–H···A H···A (Å) D···A (Å) D–H···A (◦) Salt 1
C16–Br2····S1 3.535 165.06
C7–Br1····O1 3.301 167.95 C18–H18····N9 2.835(.005) 3.742 (7) 165.51 (33) C14–H14····N7 2.483(.005) 2.636 (7) 88.96 (30) N6–H6N····S1 2.652(.001) 3.483 (4) 162.84 (23) C9–H9····N3 2.451(.004) 2.642 (7) 91.31 (33) C3–H3····N7 2.953(.004) 3.514 (6) 120.18 (26) N1–H1N····O1 1.839 (40) 2.696 (5) 173.88 (26 O1-H1O····N9 2.126 (70) 2.915 (6) 163.85 (95) O1–H2O····N9 2.035 (45) 2.843 (6) 162.72 (61) N5–H5N····N2 1.884 (3) 2.740 (5) 173.33 (26) N6–H6N····N8 2.573 (5) 2.616 (7) 83.31 (32) N5–H5N····N2 1.884 (3) 2.740 (5) 173.33 (26)
N6–H6N····π 3.55
Salt 2
C2–I1····O2 3.079 170.30
C3–H3····O4 2.724 (36) 3.278 (5) 118.00 (61) C2–H2····O1 2.467 (42) 3.340 (6) 153.95 (41) C9–H9····O3 2.640 (32) 3.728 (5) 165.01 (33) C5–H5····N3 2.490 (35) 2.751 (4) 94.51 (16) N1–H1N····O1 1.851 (43) 2.656 (5) 160.35 (15) O1–H1O····O3 1.942 (61) 2.753 (5) 175.95 ( 99) O1–H2O····O3 2.109 (52) 2.806 (5) 150.51 (24) N2–H2N····O2 1.807 (46) 2.705 (5) 173.41 (37) N2–H2N····O4 2.634 (43) 3.188 (5) 120.54 (48) O1–H2O····O2 2.779 (58) 3.405 (8) 139.87 (9) N1–H1N····N4 2.500 (40) 2.684 (4) 93.43 ( 84)
π ····πazo 3.532
Salt 3
C9–H9····O3 2.648 (4) 3.512 (5) 154.77 (23) C8–H8····O2 2.521 (4) 3.403 (6) 158.34 (26) C4–H4····N3 2.453 (3) 2.703 (5) 95.34 (24) C8–H8····O4 2.937 (4) 3.270 (6) 102.75 (26) C3–H3····O1 2.834 (5) 3.758 (6) 172.97 (24) C8–H8····O3 2.813 (4) 3.331 (6) 116.31 (26) O5–H1O····O1 2.201 (10) 3.037 (6) 129.24 (98) O5–H5O····O1 2.110 (63) 2.895 (6) 154.09 (69) N4–H4N····O5 1.988 (45) 2.773 (4) 162.80 (48) N5–H3N····O2 2.001 (41) 2.896 (5) 170.57 (75) N5–H3N····N1 2.630 (40) 2.724 (5) 86.21 (48)
C1–I1····O5 3.468 170.61
Salt 4
C12–H12····O2 2.638 (2) 3.539 (3) 163.33 (15) C7–H7····O1 2.528 (2) 3.329 (3) 144.53 (15) C2–H2····O3 2.599 (2) 3.232 (3) 125.74 (15) C3–H3····O1 2.783 (3) 3.420 (3) 126.60 (15) C12–H12····N4 2.525 (2) 2.825 (3) 99.11 (13) C5–H5····N3 2.427 (2) 2.703 (3) 96.97 (14) C10–H10····O2 2.861 (2) 3.459 (3) 123.19 (15) C7–H7····N1 2.528 (2) 3.329 (3) 144.53 (15) N1–H1N····O3 1.845 (2) 2.703 (2) 174.72 (13) N2–H2N····O1 2.364 (2) 2.913 (3) 165.98 (12) N4–H4····N2 2.613 (2) 2.729 (3) 88.46 (13)
π ····πazo 3.578
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Chapter - 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly Salt 5
C4–H4····O3 3.564 (6) 2.658 (4) 164.67 (30) N6–H6N····N1 1.815 (38) 2.685(.005) 177.74 (79) N5–H5N····O4 1.754 (50) 2.818(.004) 160.93 (49) O4–HOB····O2 1.778 (40) 2.841(.005) 170.10 (24) O4–HOA····O3 1.947 (46) 2.923(.004) 158.89 (92) N2–H2N····O1 2.340 (29) 3.166(.005) 169.47 (81) N2–H2N····O2 2.472 (30) 3.078(.005) 130.17 (53) N2–H2N····N4 2.647 (37) 2.726(.005) 86.40 (44) N5–H5N····N8 2.553 (68) 2.687(.005) 84.81 (48) O4–HOB····O3 2.346 (37) 3.139(.004) 129.41 (66) O4–HOB····N9 2.422 (40) 3.450(.006) 159.82 (86) N2–H2N····N2 2.797 (29) 3.567(.005) 154.12 (62) O4–HOA····N9 2.854 (43) 3.864(.005) 170.24 (48) C9–H9····O1 2.622 (4) 3.522 (7) 163.27 (29) C22–H22····O4 2.695 (4) 3.607 (6) 167.03 (30) C9–H9····N4 2.498 (3) 2.809 (5) 99.76 (26) C2–H2····N3 2.430 (4) 2.704 (6) 96.89 (29) C15–H15····N7 2.471 (4) 2.729 (6) 95.91 (29) C22–H22····N8 2.506 (3) 2.814 (5) 99.54 (28) C13–H13····O2 2.928 (5) 3.278 (6) 103.92 (29) C4–H4····N9 2.898 (5) 3.712 (7) 147.02 (31) C6–H6····O1 2.935 (5) 3.586 (7) 128.31 (30) C4–H4····O3 2.658 (4) 3.564 (6) 164.67 (30) C22–H22····O4 2.695 (4) 3.607 (6) 167.03 (30) C25–H25····O3 2.827 (3) 3.313 (6) 113.83 (29) C3–H3····O4 2.954 (4) 3.593 (6) 127.17 (30) C19–H19····O4 2.868 (4) 3.564 (7) 132.58 (32) C16–H16····O1 2.942 (5) 3.489 (7) 119.02 (35)
C16–H16····π 4.153
π ····πazo 3.4405
Figure 4.1.A. FT-IR spectra of L10.
Chapter - 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly
Figure 4.2.A. (a) Packing of salt 2 along a axis; (b) Hydrogen bonding pattern of crystal water and (c) NO3-
anion in salt 2.
Figure 4.3.A. (a) Hydrogen bonding pattern of crystal water; (b) Elliptical pocket for anion and water in salt 3 along a axis and (c) ClO4- anion in salt 3.
Figure 4.4.A. (a) Packing of salt 5 along a axis; (b) Packing of salt 5 along c axis; (c) Hydrogen bonding pattern of crystal water and (c) NO3- anion in salt 5.
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Chapter - 4 2-aryl azo imidazole dyes – Molecular Recognition and Self-Assembly
Figure 4.4.A. (a) UV-visible spectra of Ligands (L9-11) and UV-visible spectra of L10 in high and low pH.
Table 4.3.A. Fluorescence quantum yield of L11 with different anionic input Sr. No. Anionic input ΦF ΦF - Φq
1 Nil 0.025 0.000
2 Br- 0.019 0.006
3 Cl- 0.022 0.003
4 SCN- 0.018 0.007
5 NO3_ 0.014 0.011
6 ClO4- 0.001 0.024
7 CH3COO- 0.016 0.009
8 CF3SO3- 0.014 0.008
9 BF4- 0.020 0.005
Table 4.4.A. Fluorescence quantum yield of L11 with different concentration of ClO4-. Sr. No. [ClO4-] (M) Φq ΦF/Φq
1 4 x 10-6 0.0060 3.5000 2 8 x 10-6 0.0031 6.7000 3 12 x 10-6 0.0025 8.3000 4 16 x 10-6 0.0018 11.700 5 20 x 10-6 0.0016 13.000 6 24 x 10-6 0.0013 16.000 7 28 x 10-6 0.0011 18.900 8 32 x 10-6 0.0010 21.000