1 Electronic Supplementary Data Arylazoimidazole complexes of lead(II)-halide and their photochromism Debashis Mallick a , Bharati Chowdhury b , Chandana Sen b , Kamal Krishna Sarkar c , Srikanta Jana b , Sudipa Mondal b & Chittaranjan Sinha b, * a Department of Chemistry, Mrinalini Datta Mahavidyapith, Birati, Kolkata 700 051, India b Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700 032, India c Department of Chemistry, Mahadevananda Mahavidyalaya, SN Banerjee Rd, Monirampore, Kolkata, West Bengal 700120, India Email: [email protected] No. Contents Pg No. 1 Fig. S1 – 1 H NMR spectrum of Meaai-C 6 H 13 2 2 Fig. S2 – 1 H NMR spectrum of Meaai-C 8 H 17 2 3 Fig. S3 – 1 H NMR spectrum of [Pb(Meaai-C 6 H 13 )I 2 ] n 3 4 Fig. S4 – HRMS spectrum of [Pb(Meaai-C 6 H 13 )I 2 ] n (11b) 3 5 Fig. S5 – Spectral changes of Meaai-C 6 H 13 (2b) in MeOH upon repeated irradiation at 364 nm at 3 min interval at 25 0 C 4 6 Fig. S6 – Photochromism of Meaai-C 6 H 13 (2b) in toluene and resistance to repeated irradiation upon UV light irradiation at 362 nm for 10 min followed by irradiation of visible light at 455 nm for 10 min 4 7 Fig. S7 – The Eyring plots of rate constants of E-to –Z thermal isomerisation of [Pb(Meaai-C 6 H 13 ) I) 2 ] (11b) at different temperatures 4 8 Fig. S8 – FMOs of complexes 5b, 8b and 11b 5 9 Fig. S9 – FMOs of 11b considering cleavage of Pb-N(azo) bond upon irradiation of UV light and the formation of three coordinated Pb(II)-motif 6 10 Table S1 – 1 H NMR spectral data in DMSO-d 6 at room temperature 7 11 Table S2 – Results of photochromism, rate of conversion and quantum yields upon UV light irradiation of Raai-C n H 2n+1 in methanol at 298 K 7 12 Table S3 – Frontier MOs, their energy and composition of [Pb(Meaai-C 6 H 13 )Cl 2 ] (5b) 8 13 Table S4 – Calculated spectral transitions of [Pb(Meaai-C 6 H 13 )Cl 2 ] (5b) 8 14 Table S5 – Frontier MOs, their energy and composition of [Pb(Meaai-C 6 H 13 )Br 2 ] (8b) 9 15 Table S6 – Calculated spectral transitions of [Pb(Meaai-C 6 H 13 )Br 2 ] (8b) 9 16 Table S7 – Frontier MOs, their energy and composition of [Pb(Meaai-C 6 H 13 )I 2 ] (11b) 10 17 Table S8 – Calculated spectral transitions of [Pb(Meaai-C 6 H 13 )I 2 ] (11b) 10 18 Table S9 – Frontier MOs, their energy and composition of three cordinated [Pb(Meaai-C 6 H 13 )I 2 ] (11b) 11 19 Table S10 – Calculated spectral transitions of three cordinated [Pb(Meaai-C 6 H 13 )I 2 ] (11b) 11
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1
Electronic Supplementary Data
Arylazoimidazole complexes of lead(II)-halide and their photochromism
Debashis Mallicka, Bharati Chowdhury
b, Chandana Sen
b, Kamal Krishna Sarkar
c,
Srikanta Janab, Sudipa Mondalb & Chittaranjan Sinhab,*
aDepartment of Chemistry, Mrinalini Datta Mahavidyapith, Birati, Kolkata 700 051, India bDepartment of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700 032, India
cDepartment of Chemistry, Mahadevananda Mahavidyalaya, SN Banerjee Rd, Monirampore,
Kolkata, West Bengal 700120, India
Email: [email protected]
No. Contents Pg No.
1 Fig. S1 – 1H NMR spectrum of Meaai-C6H13 2
2 Fig. S2 –1H NMR spectrum of Meaai-C8H17 2
3 Fig. S3 –1H NMR spectrum of [Pb(Meaai-C6H13)I2]n 3
4 Fig. S4 – HRMS spectrum of [Pb(Meaai-C6H13)I2]n (11b) 3
5 Fig. S5 – Spectral changes of Meaai-C6H13 (2b) in MeOH upon repeated irradiation at 364 nm
at 3 min interval at 250C
4
6 Fig. S6 – Photochromism of Meaai-C6H13 (2b) in toluene and resistance to repeated irradiation
upon UV light irradiation at 362 nm for 10 min followed by irradiation of visible light at
455 nm for 10 min
4
7 Fig. S7 – The Eyring plots of rate constants of E-to –Z thermal isomerisation of
[Pb(Meaai-C6H13) I)2] (11b) at different temperatures
4
8 Fig. S8 – FMOs of complexes 5b, 8b and 11b 5
9 Fig. S9 – FMOs of 11b considering cleavage of Pb-N(azo) bond upon irradiation of UV light
and the formation of three coordinated Pb(II)-motif
6
10 Table S1 –1H NMR spectral data in DMSO-d6 at room temperature 7
11 Table S2 – Results of photochromism, rate of conversion and quantum yields upon UV light
irradiation of Raai-CnH2n+1 in methanol at 298 K 7
12 Table S3 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)Cl2] (5b) 8
13 Table S4 – Calculated spectral transitions of [Pb(Meaai-C6H13)Cl2] (5b) 8
14 Table S5 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)Br2] (8b) 9
15 Table S6 – Calculated spectral transitions of [Pb(Meaai-C6H13)Br2] (8b) 9
16 Table S7 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)I2] (11b) 10
17 Table S8 – Calculated spectral transitions of [Pb(Meaai-C6H13)I2] (11b) 10
18 Table S9 – Frontier MOs, their energy and composition of three cordinated
[Pb(Meaai-C6H13)I2] (11b)
11
19 Table S10 – Calculated spectral transitions of three cordinated [Pb(Meaai-C6H13)I2] (11b) 11
2
Fig. S1 – 1H NMR spectrum of Meaai-C6H13
Fig. S2 –1H NMR spectrum of Meaai-C8H17
3
Fig. S3 –1H NMR spectrum of [Pb(Meaai-C6H13)I2]n
Fig. S4 – HRMS spectrum of [Pb(Meaai-C6H13)I2]n (11b)
4
300 350 400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
1.2
300 350 400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
Isobestic point
323 nm
433 nm
Trans-isomer
cis-isomer
Ab
so
rban
ce
Wavelength(nm)
323 nm
433 nm
Isobestic pointIncreasing
Decreasing
Ab
so
rban
ce
Wavelength(nm)
Fig. S5 – Spectral changes of Meaai-C6H13 (2b) in MeOH upon repeated irradiation at 364 nm at 3 min interval at 250C
Fig. S6 – Photochromism of Meaai-C6H13 (2b) in toluene and resistance to repeated irradiation upon UV light irradiation at
362 nm for 10 min followed by irradiation of visible light at 455 nm for 10 min
3.2x10-3
3.3x10-3
3.3x10-3
3.3x10-3
3.4x10-3
13.25
13.50
13.75
14.00
14.25
14.50
3.2x10-3
3.3x10-3
3.3x10-3
3.3x10-3
3.4x10-3
13.25
13.50
13.75
14.00
14.25
14.50
-Ln
K/T
1/T Fig. S7 – The Eyring plots of rate constants of E-to –Z thermal isomerisation of [Pb(Meaai-C6H13) I)2] (11b) at different
temperatures
5
5b 8b 11b
LUMO+2
E-0.55 (Pb,22%;Cl,3%;L,75%) E-0.73eV (Pb,45%;Br,10%,L,45%) E-1.01eV(Pb,34%;I,9%,L,57%)
LUMO+1
E--0.94 (Pb,1%;Cl,0%;L,98%) E-1.03eV(Pb,3%;Br,1%,L,96%) E-1.12eV (Pb,31%;I,9%,L,60%)
LUMO
E-3.45eV(Pb,1%;Cl,1%,L,98%) E-3.55eV(Pb,0%;Br,2%,L,98%) E-3.64eV(Pb,0%;I,2%,L,97%)
HOMO
E-6.17eV(Pb,19%;Cl,74%;L,7%) E-5.94eV(Pb,12%;Br,84%,L,4%) E-5.65eV(Pb,4%;I,94%,L,1%)
HOMO-1
E-6.46eV(Pb,2%;Cl,97%;L,2%) E-6.07eV(Pb,2%;Br,97%,L,1%) E-5.75eV(Pb,6%;I,93%,L,2%)
HOMO-2
E -6.58 eV(Pb,0%;Cl,94%;L,5%) E-6.22eV(Pb,0%;Br,98%,L,2%) E-5.87eV(Pb,0%;I,98%,L,2%)
Fig. S8 – FMOs of complexes 5b, 8b and 11b
6
LUMO+2, E = -1.01 eV, , Pb, 28%,
MeaaiC6H13, 64%, I, 8%
LUMO+1 , E = -1.13 eV, , Pb:37%,
MeaaiC6H13, 53%, I, 10%.
LUMO, E = -3.64 eV; MeaaiC6H13,
98%, I, 2%
HOMO, E: -5.66 eV, , Pb:4%,
MeaaiC6H13, 1%; I, 95%
HOMO-1; E: -5.77 eV, , Pb, 6 %;
MeaaiC6H13, 2%; I, 92%.
HOMO-2,E: -5.87 eV, Pb:1%;
MeaaiC6H13, 2%; I, 98%.
Fig. S9 – FMOs of 11b considering cleavage of Pb-N(azo) bond upon irradiation of UV light and the formation of three
coordinated Pb(II)-motif
7
Table S1 –1H NMR spectral data in DMSO-d6 at room temperature
Compounds 4-Hs 5-H
s 7,11-H
d
8,10-Hd 9-R
s 12-CH2
t CH3
t† CH3- (CH2)*
-CH2-bs†
[Pb(Haai-C4H9)Cl2](4a) 7.70 7.28 7.81
(8.4)
7.54 7.55 4.53
(6.3)
0.87
(6.2)
1.04-1.12
[Pb(Meaai-C4H9)Cl2] (4b) 7.68 7.27 7.79
(7.4)
7.53 2.43 4.49
(7.1)
0.88
(6.3)
1.03-1.24
[Pb(Haai-C6H13)Cl2] (5a) 7.68 7.29 7.84
(8.3)
7.51 7.57 4.56
(6.4)
0.87
(6.2)
1.01-1.12
[Pb(Meaai-C6H13)Cl2] (5b) 7.69 7.28 7.79 (7.5) 7.52 2.42 4.47
(7.0)
0.87
(6.2)
1.03-1.23
[Pb(Meaai-C8H17)Cl2] (6a) 7.68 7.29 7.83
(7.8)
7.51 7.59 4.54
(6.3)
0.85
(6.2)
1.07-1.10
[Pb(Haai-C8H17)Cl2] (6b) 7.68 7.27 7.76
(7.7)
7.50 2.43 4.49
(7.1)
0.81
(6.2)
1.04-1.07
[Pb(Haai-C4H9)Br2] (7a) 7.68 7.27 7.81
(8.5)
7.53 7.58 4.53
(6.3)
0.86
(6.2)
1.02-1.24
[Pb(Meaai-C4H9)Br2] (7b) 7.65 7.25 7.80
(7.4)
7.51 2.42 4.49
(7.0)
0.87
(6.2)
1.02-1.23
[Pb(Haai-C6H13)Br2] (8a) 7.63 7.27 7.81
(8.3)
7.53 7.56 4.56
(6.4)
0.86
(6.3)
1.03-1.14
[Pb(Meaai-C6H13)Br2] (8b) 7.64 7.26 7.79
(7.4)
7.51 2.41 4.48
(7.01)
0.87
(6.2)
1.01-1.23
[Pb(Meaai-C8H17)Br2] (9a) 7.68 7.28 7.82
(7.8)
7.53 7.58 4.53
(6.3)
0.85
(6.2)
1.09-1.15
[Pb(Haai-C8H17)Br2] (9b) 7.62 7.28 7.75
(7.7)
7.52 2.43 4.47
(7.3)
0.83
(6.4)
1.04-1.22
[Pb(Haai-C4H9)I2]n(10a) 7.58 7.28 7.81
(8.3)
7.51 7.55 4.53
(6.3)
0.86
(6.1)
1.02-1.12
[Pb(Meaai-C4H9)I2] (10b) 7.57 7.26 7.79
(7.4)
7.51 2.41 4.49
(7.0)
0.86
(6.2)
1.02-1.24
[Pb(Haai-C6H13)I2] (11a) 7.57 7.29 7.80
(8.2)
7.50 7.58 4.55
(6.4)
0.87
(6.2)
1.01-1.12
[Pb(Meaai-C6H13)I2] (11b) 7.56 7.27 7.78
(7.4)
7.50 2.40 4.49
(7.0)
0.86
(6.2)
1.02-1.23
[Pb(Heaai-C8H17)I2] (12b) 7.58 7.27 7.81
(7.8)
7.52 7.59 4.52
(6.3)
0.86
(6.2)
1.09-1.10
[Pb(Meaai-C8H17)I2] (12b) 7.57 7.26 7.76
(7.6)
7.51 2.42 4.48
(7.1)
0.84
(6.2)
1.03-1.02
sSinglet; dDoublet; tTriplet; bsBroad Singlet; †last -CH3 of respective N-alkyl group
Table S2 – Results of photochromism, rate of conversion and quantum yields upon UV light irradiation of Raai-CnH2n+1 in
methanol at 298 K
Compds λπ,π* (nm) Isobestic point (nm) Rate of E→Z conversion x 109
(s-1)
φE→Z
conversion x 109
1a 363 328, 437 36.01 1.90± 0.005
1b 362 327, 430 35.71 1.87 ± 0.002
2a 363 325, 435 34.92 1.81± 0.001
2b 364 323, 433 34.09 1.79± 0.003
3a 364 330, 427 33.76 1.69± 0.004
3b 365 324, 435 32.14 1.65± 0.002
8
Table S3 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)Cl2] (5b)
Orbital Energy(eV) Composition(%)
Pb Chloride ligand
LUMO+10 2.48 1 0 99
LUMO+9 2.34 0 0 100
LUMO+8 2.09 0 0 100
LUMO+7 0.95 14 1 85
LUMO+6 0.5 79 8 13
LUMO+5 0.19 60 8 31
LUMO+4 0.02 55 3 42
LUMO+3 -0.25 35 4 62
LUMO+2 -0.55 22 3 75
LUMO+1 -0.94 1 0 98
LUMO -3.45 1 1 98
HOMO -6.17 19 74 7
HOMO-1 -6.46 2 97 2
HOMO-2 -6.58 0 94 5
HOMO-3 -6.68 3 82 16
HOMO-4 -6.8 1 12 88
HOMO-5 -6.9 11 74 15
HOMO-6 -7.41 10 50 40
HOMO-7 -7.66 0 1 98
HOMO-8 -7.91 13 49 39
HOMO-9 -8.08 0 0 99
HOMO-10 -8.72 1 1 98
Table S4 – Calculated spectral transitions of [Pb(Meaai-C6H13)Cl2] (5b)
Eexcitation (eV) λexcitation (nm) Oscillator
strength (f)
Key transition Character
2.4290 510.43 0.0104 (64%)HOMO-1→LUMO XLCT
2.9885 414.88 0.5952 (66%)HOMO→LUMO XLCT,
MLCT
3.1262 396.60 0.2226 (60%)HOMO-2→LUMO XLCT
3.4913 355.13 0.0291 (56%)HOMO-4→LUMO ILCT, XLCT
4.4633 277.79 0.0535 (95%)HOMO-9→LUMO ILCT
5.2169 237.66 0.0617 (83%)HOMO→LUMO+1 XLCT,
MLCT
9
Table S5 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)Br2] (8b)
Orbital Energy(eV) Composition
Pb Bromide ligand
LUMO+10 2.45 0 0 100
LUMO+9 2.29 0 0 100
LUMO+8 2.05 0 0 100
LUMO+7 0.86 6 1 93
LUMO+6 0.26 77 11 12
LUMO+5 -0.05 15 3 82
LUMO+4 -0.28 81 9 11
LUMO+3 -0.41 28 3 69
LUMO+2 -0.73 45 10 45
LUMO+1 -1.03 3 1 96
LUMO -3.55 0 2 98
HOMO -5.94 12 84 4
HOMO-1 -6.07 2 97 1
HOMO-2 -6.22 0 98 2
HOMO-3 -6.33 3 92 4
HOMO-4 -6.57 15 75 10
HOMO-5 -6.86 0 1 99
HOMO-6 -7.23 13 66 20
HOMO-7 -7.75 0 0 100
HOMO-8 -7.79 10 23 67
HOMO-9 -8.17 0 0 100
HOMO-10 -8.77 1 1 98
Table S6 – Calculated spectral transitions of [Pb(Meaai-C6H13)Br2] (8b)
Eexcitation (eV) λexcitation (nm) Oscillator
strength (f)
Key transition Character
2.8662 452.58 0.0723 (28%)HOMO-2→LUMO XLCT
2.9861 415.21 0.6390 (52%)HOMO→LUMO XLCT,
MLCT
3.1269 396.51 0.0581 (81%)HOMO-3→LUMO XLCT
4.1621 297.89 0.0323 (49%)HOMO-9→LUMO ILCT
4.9962 248.16 0.0873 (64%)HOMO-1→LUMO+1 XLCT
10
Table S7 – Frontier MOs, their energy and composition of [Pb(Meaai-C6H13)I2] (11b)
Orbital Energy(eV) Composition
Pb Iodide ligand
LUMO+10 2.41 0 0 100
LUMO+9 2.24 0 0 100
LUMO+8 2.0 0 0 100
LUMO+7 0.74 3 0 97
LUMO+6 -0.0 69 10 21
LUMO+5 -0.18 19 3 78
LUMO+4 -0.53 13 1 86
LUMO+3 -0.63 83 9 8
LUMO+2 -1.01 34 9 57
LUMO+1 -1.12 31 9 60
LUMO -3.64 0 2 97
HOMO -5.65 4 94 1
HOMO-1 -5.75 6 93 2
HOMO-2 -5.87 0 98 2
HOMO-3 -6.01 3 94 3
HOMO-4 -6.29 18 75 8
HOMO-5 -6.91 5 23 72
HOMO-6 -6.98 13 51 36
HOMO-7 -7.81 3 3 93
HOMO-8 -7.82 5 6 88
HOMO-9 -8.25 0 0 100
HOMO-10 -8.83 1 1 99
Table S8 – Calculated spectral transitions of [Pb(Meaai-C6H13)I2] (11b)
Eexcitation (eV) λexcitation (nm) Oscillator
strength (f)
Key transition Character
2.6641 465.39 0.0166 (59%)HOMO-3→LUMO XLCT
2.9756 416.67 0.7729 (80%)HOMO-2→LUMO XLCT
3.4412 360.29 0.0277 (96%)HOMO-7→LUMO ILCT
4.1837 330.28 0.0238 (84%)HOMO-9→LUMO ILCT
4.4254 280.16 0.0791 (68%)HOMO-10→LUMO ILCT
4.9464 250.65 0.0739 (42%)HOMO→LUMO+3 XMCT
N.B: Metal to ligand charge transfer(MLCT); Ligand to metal charge transfer(LMCT); Intra ligand charge transfer(ILCT);
Halide(X) to metal charge transfer(XMCT); Halide(X) to ligand charge transfer(XLCT)
11
Table S9 – Frontier MOs, their energy and composition of three cordinated [Pb(Meaai-C6H13)I2] (11b)
Orbital Energy(eV) Composition
Pb Iodide ligand
LUMO+10 2.46 1 0 99
LUMO+9 2.26 0 0 100
LUMO+8 2.05 0 0 100
LUMO+7 0.74 4 0 96
LUMO+6 -0.03 71 10 19
LUMO+5 -0.17 18 2 80
LUMO+4 -0.53 8 1 90
LUMO+3 -0.62 97 09 04
LUMO+2 -1.01 28 8 64
LUMO+1 -1.13 37 10 53
LUMO -3.64 00 02 97
HOMO -5.66 04 95 01
HOMO-1 -5.77 06 92 02
HOMO-2 -5.87 01 98 02
HOMO-3 -6.02 03 94 03
HOMO-4 -6.30 17 75 08
HOMO-5 -6.91 06 27 68
HOMO-6 -6.98 12 47 41
HOMO-7 -7.81 00 00 100
HOMO-8 -7.83 09 10 81
HOMO-9 -8.25 00 00 100
HOMO-10 -8.79 01 00 99
Table S10 – Calculated spectral transitions of three cordinated [Pb(Meaai-C6H13)I2] (11b)
Eexcitation (eV) λexcitation (nm) Oscillator
strength (f)
Key transition Character
2.6206 473.12 0.0258 (45%)HOMO-6→LUMO XLCT
3.0844 401.97 0.0243 (78%)HOMO-5→LUMO LLCT
3.1623 392.07 0.6419 (49%)HOMO-6→LUMO XLCT
3.5240 351.83 0.0281 (95%)HOMO-7→LUMO LLCT
3.9145 316.73 0.0193 (69%)HOMO→LUMO+1 XLCT
4.2394 292.46 0.0132 (43%)HOMO→LUMO+3 XMCT
N.B: Metal to ligand charge transfer (MLCT); Ligand to metal charge transfer (LMCT); Intra ligand charge transfer (ILCT);
Halide (X) to metal charge transfer (XMCT); Halide(X) to ligand charge transfer (XLCT)
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