1400
1200
1000
800
600
400
200
0
0
REZA TAKJOO* a , PONNADURAI RAMASAMI* b,c , JOEL T. MAGUE d , ZOHREH HASANI a and
LYDIA RHYMAN b
1600
500 3500 4000 1000 1500 2000
Frequency (cm
-1
)
2500
Figure SI1. Simulated IR spectra of 1 .
3000
1

900
800
700
600
500
400
300
200
100
0
0 500 1000 1500 2000
Frequency (cm
-1
2500
)
Figure SI2. Simulated IR spectra of 2 .
3000 3500 4000
2

1400
1200
1000
800
600
400
200
0
0 500 1000 1500 2000
Frequency (cm
-1
)
2500
Figure SI3. Simulated IR spectra of 3 .
3000 3500 4000
3

800
700
600
500
400
300
200
100
0
0 500 1000 1500 2000
Frequency (cm
-1
)
2500
Figure SI4. Simulated IR spectra of 4 .
3000 3500 4000
4

b
Figure SI5. One-dimensional ribbon viewed along the b axis for 1 . Hydrogen bonds are shown as dotted blue lines.
5

Figure SI6. Dimer of 2 formed by O5-H5O∙∙∙N2 hydrogen bonds. Hydrogen bonds are shown as dotted blue lines.
6

b
Figure SI7. One-dimensional ribbon viewed along the b axis for 2 . Hydrogen bonds are shown as dotted blue lines.
7

Figure SI8. Dimer of 3 formed by N3-N3H∙∙∙O3 hydrogen bonds. Hydrogen bonds are shown as dotted blue lines.
8

Figure SI9. One-dimensional ribbon viewed along the b axis for 3 . Hydrogen bonds and chalcogen-chalcogen interactions are shown as dotted blue and red lines respectively.
9

Figure SI10. Dimer of 4 formed by N3-H3N∙∙∙O3 hydrogen bonds. Hydrogen bonds are shown as dotted blue lines.
10

Figure SI11. One-dimensional ribbon viewed along bisector of the b and c axes for 4 . Hydrogen bonds are shown as blue dotted lines (N6 belongs to acetonitrile molecule).
Compound 1 :
Weak C12-H12B∙∙∙O3 c
( c
x , y , 1z ) hydrogen bonding holds the chains (see figure SI5) together along the c axis (figure i). Additionally intermolecular, C5-H5∙∙∙O2 d (2.521 Å) ( d 1x , 1y , 2z ) and C4-H4∙∙∙O3 e
(2.626 Å) ( e
1+ x , 1+ y , z ) hydrogen bonds generate the three-dimensional network (figure ii).
11

Figure i. Two-dimensional sheet viewed in the bc plane for 1 . Hydrogen bonds are shown as blue dotted lines.
Figure ii. Three-dimensional supramolecular network of 1 (View down the b axis). Hydrogen bonds are shown as blue dotted lines.
12

Compound 2 :
These ribbons (see figure SI7) are linked by means of C12-H12B∙∙∙O1 i , C12-H12B∙∙∙O4 i ( i 2x ,
1y , 2z ) and C12-H12C∙∙∙C4 j
( j
2x , 2y , 2z ) hydrogen bonds forming a two-dimensional sheet
(figure iii). As shown in figure ix, a supramolecular structure is completed with N3-N3H∙∙∙O2 k
( k
2x , 1y , 1z ) intermolecular hydrogen bonding.
Figure iii. Two-dimensional sheet for 2 . Hydrogen bonds are shown as blue dotted lines.
Figure iv. Three-dimensional supramolecular network of 2 . Hydrogen bonds are shown as blue dotted lines.
13

Compound 3 :
Weak C-H∙∙∙O interactions generate two dimensional sheets along the c axis as shown in figure v. Further weak C-H∙∙∙O and C-H∙∙∙π
(C10=C11)
interactions complete three-dimensional network (figure vi).
Figure v. Two-dimensional sheet for 3 (view down the b axis). Hydrogen bonds are shown as blue dotted lines.
Figure vi. Three-dimensional supramolecular network of 3 . Hydrogen bonds are shown as blue dotted lines.
14

Compound 4 :
These chains (see figure SI11) are attached to each other with C4-H4∙∙∙O1 t , C4-H4∙∙∙O4 t ,
C5-H5A∙∙∙C12 t
( t ½x
, ½+ y
, ½z ), C12-H12B∙∙∙N6 u
( u
x , y , 1z ), C3-H3∙∙∙O2 t
and C3-H3∙∙∙O3 t
( t ½x
, ½+ y
, ½z ) hydrogen bonds (figure vii). Expansion of this chain to a three-dimensional structure occurs via C14-H14∙∙∙O4 v
, C16-H16A∙∙∙O3 v
( v
x , y , z ), C11-H11B∙∙∙O2 w
,
C10-H10∙∙∙C8 w
( w
1x , y , z ) and C18-H18A∙∙∙O2 t
( t ½x
, ½+ y
, ½z ) hydrogen bonds (figure viii).
Figure vii. Two-dimensional sheet of 4 . Hydrogen bonds are shown as blue dotted lines.
15

Figure viii. Three-dimensional supramolecular network of 4 . Hydrogen bonds are shown as blue dotted lines.
16

TD spectrum
0.28
0.27
0.26
0.25
0.24
0.23
0.22
0.21
0.2
0.19
0.18
0.17
0.16
0.15
0.14
0.13
0.12
0.11
0.1
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0.37
0.36
0.35
0.34
0.33
0.32
0.31
0.3
0.29
260 280 300 320 340 360 380 400 420
Wavelength, nm
440 460 480 500 520 540 560
Figure SI12. Simulated electronic spectra of 1 in ethanol.
17

TD spectrum
0.16
0.15
0.14
0.13
0.12
0.11
0.1
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
260
0.21
0.2
0.19
0.18
0.17
0.26
0.25
0.24
0.23
0.22
0.33
0.32
0.31
0.3
0.29
0.28
0.27
280 300 320 340 360 380 400 420
Wavelength, nm
440 460 480 500 520 540 560
Figure SI13. Simulated electronic spectra of 2 in ethanol.
18

TD spectrum
0.12
0.1
0.08
0.06
0.24
0.22
0.2
0.18
0.16
0.14
0.04
0.02
0
280
0.38
0.36
0.34
0.32
0.3
0.28
0.26
0.5
0.48
0.46
0.44
0.42
0.4
300 320 340 360 380 400 420 440
Wavelength, nm
460 480 500 520 540 560 580
Figure SI14. Simulated electronic spectra of 3 in ethanol.
19

TD spectrum
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
280
0.15
0.14
0.13
0.12
0.11
0.1
0.21
0.2
0.19
0.18
0.17
0.16
0.34
0.33
0.32
0.31
0.3
0.29
0.28
0.27
0.39
0.38
0.37
0.36
0.35
0.26
0.25
0.24
0.23
0.22
300 320 340 360 380 400 420 440
Wavelength, nm
460 480 500 520 540 560 580
Figure SI15. Simulated electronic spectra of 4 in ethanol.
20

Complex 1
HOMO
Complex 2
LUMO
HOMO
Complex 3
LUMO
HOMO
21
LUMO

Complex 4
HOMO LUMO
Figure SI16. Frontier molecular orbitals of 1 4 .
Table SI1. Angles around the metal in 1 4 .
Compound
O1-Mo1-O2
1 2 3 4
97.54(7) 98.64(7) 96.23(5) 94.02(5)
N1-Mo1-O2
N3-Mo1-O2
95.66(7) 94.85(7) 94.01(5) 89.74(6)
98.23(8) 98.16(7) 99.11(6) 101.52(6)
O3-Mo1-O2 104.60(8) 104.30(7) 104.87(6) 105.43(6)
O1-Mo1-O5/N4 79.01(6) 79.20(6) 79.64(5) 76.30(5)
N1-Mo1-O5/N4 77.38(6) 78.09(6) 77.72(5) 81.54(5)
N3-Mo1-O5/N4 82.04(7) 80.79(6) 81.23(5) 83.77(6)
O3-Mo1-O5/N4 82.70(7) 82.87(6) 83.89(5) 85.07(5)
O1-Mo1-N1
N1-Mo1-N3
N3-Mo1-O3
81.27(6)
70.88(7)
96.03(8)
81.07(6)
70.85(6)
96.19(7)
81.58(5)
70.76(5)
93.76(6)
82.01(5)
70.55(6)
93.78(6)
O3-Mo1-O1
O1-Mo1-N3
105.44(7) 105.41(7) 107.99(5) 108.74(5)
149.11(7) 148.28(6) 149.10(5) 148.15(6)
N1-Mo1-O3 157.40(7) 158.38(7) 157.44(5) 160.31(6)
O2-Mo1-O5/N4 172.59(7) 172.83(6) 171.17(5) 167.72(6)
* N4 instead of O5 in 4 .
22