Synthesis, crystal structures, photophysical properties, and bioimaging of living cells of bis-β-diketonate phenothiazine ligands and its cyclic dinuclear complexes

Article abstract of DOI:10.1021/ic200150h

Two bis-β-diketones, RCOCH₂CO-EPTZ-COCH₂COR (EPTZ = 10-ethylphenothiazine; R = C₆H₅ for H ₂L¹ and CF₃ for H₂L²) and their cyclic dinuclear Zn(II), Cd(II), N

Full text of DOI:10.1021/ic200150h

Supporting Information:
Synthesis, Crystal Structures, Photophysical Properties and Bioimaging of
Living Cells of Bis-β-Diketonate Phenothiazine Ligands and its Cyclic
Dinuclear Complexes
Dongmei Li,† Xiaohe Tian,‡ Guiju Hu,† Qiong Zhang,† Peng Wang,† Pingping Sun,† Hongping Zhou,†
Xiangming Meng,† Jiaxiang Yang,† Jieying Wu,† Baokang Jin,† Shengyi Zhang,† Xutang Tao, ┴ Yupeng
Tian,*,†,┴,║
†Department of Chemistry, Key Laboratory of Functional Inorganic Materials of Chemistry of Anhui Province, Anhui
‡
University, Hefei 230039, P.R. China; Department of Biomedical Science, University of Sheffield, Sheffield, UK;
┴State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, P.R. China; ║State Key Laboratory of
Coordination Chemistry, Nanjing University Nanjing 210093, P. R. China
Part 1 Synthesis of the complexes ................................................................................................................................ S3
1. Cd2Py4L1 (2).............................................................................................................................................................. S3
2
2. [Ni2Py4L1 ]·3C6H6 (3). .............................................................................................................................................. S3
2
3. Mn2Py4L1 (4)............................................................................................................................................................. S3
2
4. [Cu2L1 ]·2DMF (5)..................................................................................................................................................... S3
2
5. Co2Py4L1 (6).............................................................................................................................................................. S3
2
6. Cd2Py4L2 (8).............................................................................................................................................................. S4
2
7. Ni2Py4L2 (9)............................................................................................................................................................... S4
2
8. Mn2Py4L2 (10)........................................................................................................................................................... S4
2
9. [Cu2Py2L2 ]·2C6H6 (11).............................................................................................................................................. S4
2
10. Co2Py4L2 (12).......................................................................................................................................................... S5
2
Part 2 Crystal Structure Determinations .................................................................................................................... S5
Figure S1. (a) View showing the 1D column along the a-axis of complex 7. Inset: showing 1D channels. (b) 1D
columns interacted with each other through edge-to-face π-π interactions to generate a 3D structure (Black
balls represent the centroids of benzene rings). .................................................................................................. S6
Figure S2. (a) The ORTEP structure of [Zn2Py4L1 ]·2Py (1) (50% thermal ellipsoid probability). (b) View showing
2
the 1D column along the b-axis. All hydrogen atoms are omitted for clarity.................................................................. S7
Figure S3. The ORTEP structure of 8 (50% thermal ellipsoid probability). All hydrogen atoms and solvents molecules
are omitted for clarity. ..................................................................................................................................................... S7
Figure S4. The ORTEP structure of 9 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
......................................................................................................................................................................................... S7
Figure S5. The ORTEP structure of 10 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
......................................................................................................................................................................................... S8
S1

Figure S6. The ORTEP structure of 11 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
......................................................................................................................................................................................... S8
Figure S7. The ORTEP structure of 12 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
......................................................................................................................................................................................... S8
Table S1. Crystal data and structure refinement parameters for the compounds H2L1, 1, 7 and 8................................. S9
Table S2. Crystal data and structure refinement parameters for 9-12............................................................................. S9
Table S3. Selected bond lengths [Å] and angles [º] for H2L1....................................................................................... S10
Table S4. Selected bond lengths [Å] and angles [º] for complex 7. ............................................................................. S10
Table S5. Selected bond lengths [Å] and angles [º] for complex 1. ............................................................................. S11
Table S6. Selected bond lengths [Å] and angles [º] for complex 8. ............................................................................. S11
Part 3 ............................................................................................................................................................................ S12
Figure S8. Linear absorption (left) and OPEF (right) spectra of H2L1 in six solvents, c = 10 µM.............................. S12
Figure S9. Linear absorption (left) and OPEF (right) spectra of H2L2 in six solvents, c = 10 µM.............................. S12
Figure S10. Linear absorption (left) and OPEF (right) spectra of H2L1 in six solvents, c = 1.0 µM........................... S12
Figure S11. Spatial plots of the selected frontier molecular orbitals of the enol form of (L2)2−. The time−dependent
hybrid density functional theory (TDDFT) calculations were performed using B3LYP /6-31G*//6-31G**................ S13
Figure S12. Linear absorption (left) and OPEF (right) spectra of H2L2, (L2)2− and its complexes in THF, c = 10 µM.
....................................................................................................................................................................................... S13
Table S7. Photophysical data of all the compounds ..................................................................................................... S14
Part 4 ............................................................................................................................................................................ S15
Figure S13. Log-Log linear of squared dependence of induced fluorescence signal and incident irradiance intensity of
two ligands and complexes 1, 2, 7 and 8....................................................................................................................... S15
Part 5 ............................................................................................................................................................................ S16
Table S8. Cell viability (%) of HeLa cells after incubation for 24 h with different concentration of the chromophores
....................................................................................................................................................................................... S16
Figure S14. The variable temperature 1H NMR of Zn2Py2L2 . .................................................................................. S16
2
Figure S15. MALDI-TOF Mass spectrometry of 7 ...................................................................................................... S17
References ................................................................................................................................................................... S17
S2

Part 1 Synthesis of the complexes
The synthetic route: M(OAc)2·nH2O (0.13 mmol) and bis-β-diketones (0.06 mmol) were dissolved in
5 mL of pyridine. The solution was stirred at room temperature until a lot of precipitation formed and
then filtered. The crude product was washed by dichloromethane (15 mL × 3) and then CH3CN (15 mL
× 3).
1. Cd2Py4L1 (2).
2
1
Orange solid was obtained by above synthetic route, yield: 38 mg (80%). H NMR (400 MHz, d6-
DMSO) δ (ppm): 1.35 (t, J = 6.5 and 6.5 Hz, 6H), 4.00 (q, J = 6.3, 6.0 and 6.3 Hz, 4H), 6.50 (s, 4H),
6.99 (d, J = 8.5 Hz, 4H), 7.41 (m, 20H), 7.72 (s, 4H), 7.79 (m, 8H), 7.93 (d, J = 6.5 Hz, 8H), 8.58 (s,
13
8H). C NMR (100 MHz, d6-DMSO) δ (ppm): 12.84, 42.13, 92.05, 115.02, 122.02, 124.43, 126.34,
127.06, 127.369, 128.56, 130.57, 136.72, 142.391, 145.50, 150.05, 184.10, 185.52. IR (KBr) (cm−1):
2983 and 2925 (νC–H, aliphatic), 1588 (νC=O, carbonyl), 758 and 700 (γC–H, pyridine). Anal. calcd for
C84H66Cd2N6O8S2: C, 64.00; H, 4.22; N, 5.33; O, 8.12; S, 4.07 %. Found: C, 64.08; H, 4.13; N, 5.24; O,
8.31; S, 4.15 %. TGA analysis: the first weight loss occurred at 180 °C corresponding to the loss of four
coordinated pyridine units (20.0 %). The main structure decomposed at 371 °C.
2. [Ni2Py4L1 ]·3C6H6 (3). 1
2
3. Mn2Py4L1 (4).
2
Orange solid was obtained by above synthetic route, yield: 38 mg (80 %). IR (KBr) (cm−1): 2983 and
2925 (νC–H, aliphatic), 1593 (νC=O, carbonyl), 762 and 797 (γC–H, pyridine). Anal. Calcd. for
C84H66Mn2N6O8S2: C, 69.03; H, 4.55; N, 5.75; O, 8.76; S, 4.39 %. Found: C, 68.97; H, 4.62; N, 5.81; O,
8.82; S, 4.45%. TGA analysis: the first weight loss occurred at 190 °C corresponding to the loss of four
coordinated pyridine units (21.6 %). The main structure decomposed at 410 °C.
4. [Cu2L1 ]·2DMF (5).1
2
5. Co2Py4L1 (6).
2
Orange solid was obtained by above synthetic route, yield: 40 mg (91 %). IR (KBr) (cm−1): 2976 and
2926 (νC–H, aliphatic), 1591 (νC=O, carbonyl), 758 and 699 (γC–H, pyridine). Anal. Calcd. for
C84H66Co2N6O8S2: C, 68.66; H, 4.53; N, 5.72; O, 8.71; S, 4.36%. Found: C, 68.57; H, 4.59; N, 5.80; O,
8.65; S, 4.42%. TGA analysis: the first weight loss occurred at 180 °C corresponding to the loss of four
coordinated pyridine units (21.8 %). The main structure decomposed at 410 °C.
S3

6. Cd2Py4L2 (8).
2
H2L2 (0.20 mmol, 0.10 g) in 5 mL of pyridine was added into a 50 mL colorimetric tube, layered
with 15 mL benzene, and then a solution of Cd(OAc)2·H2O (0.40 mmol, 0.2 mg) in pyridine (5 mL).
Orange single crystals for X-ray analysis were obtained on the walls of the vial in a few days, yield: 56
mg (35 %). Anal. calcd for C64H46Cd2F12N6O8S2 C, 49.78; H, 3.00; N, 5.44; O, 8.29; S, 4.15 %. Found:
C, 49.67; H, 3.03; N, 5.56; O, 8.20; S, 4.07 %. IR (KBr) (cm−1): 2981 and 2933 (νC–H, aliphatic), 1620
1
(νC=O, carbonyl), 1131 (νC–F, trifluoromethyl), 785 (γC–H, aromatic), 751 and 700 (γC–H, pyridine). H
NMR (400 MHz, d6-DMSO) δ (ppm): 1.31 (t, 6H), 3.98 (q, 4H), 6.81 (s, 4H), 7.07 (d, 4H), 7.39 (m, 8H),
13
7.53 (m, 4H), 7.79 (t, 4H), 7.93(s, 4H), 8.58 (d, 8H). C NMR (100 MHz, d6-DMSO) δ (ppm): 12.70,
42.32, 89.68, 115.45, 122.09, 124.41, 126.25, 127.83, 134.21, 136.70, 146.45, 150.07, 162.77, 178.22.
TGA analysis: the first weight loss occurred at 180°C corresponding to the loss of four coordinated
pyridine units (20.4 %). The main structure decomposed at 390 °C.
7. Ni2Py4L2 (9).
2
Above crude product again dissolved in THF/acetonitrile (v/v 3/1), orange, plate crystals were
obtained, yield: 20 mg (47 %). IR (KBr) (cm−1): 2979 and 2923 (νC–H, aliphatic), 1618 (νC=O, carbonyl),
1137 (νC–F, trifluoromethyl), 758 and 698 (γC–H, pyridine). Anal. Calcd. for C64H46F12N6Ni2O8S2: C,
53.51; H, 3.23; N, 5.85; O, 8.91; S, 4.46%. Found: C, 53.46; H, 3.19; N, 5.94; O, 8.96; S, 4.39%. TGA
analysis: the first major weight loss occurred at 180 °C corresponding to the loss of coordinated
pyridine units (21.9 %). The main structure decomposed at 426 °C.
8. Mn2Py4L2 (10).
2
Orange, plate crystals were obtained through the same way as that of 9, yield: 25 mg (58 %). IR (KBr)
(cm-1): 2982 and 2933 (νC–H, aliphatic), 1613 (νC=O, carbonyl), 1132 (νC–F, trifluoromethyl), 753 and
700 (γC–H, pyridine). Anal. Calcd. for C64H46F12Mn2N6O8S2: C, 53.79; H, 3.24; N, 5.88; O, 8.96; S,
4.49%. Found: C, 53.67; H, 3.35; N, 5.79; O, 9.02; S, 4.40%. TGA analysis: the first major weight loss
occurred at 190 °C corresponding to the loss of coordinated pyridine units (22.1 %). The main structure
decomposed at 380 °C.
9. [Cu2Py2L2 ]·2C6H6 (11).
2
H2L2 (0.06 mmol) in 5 mL of pyridine was added into a 50 mL colorimetric tube, layered with 15 mL
benzene, and then a solution of Cu(OAc)2·H2O (0.13 mmol) in pyridine (5 mL). Red crystals were
obtained on the walls of the vial in a few days, yield: 33 mg (77 %). IR (KBr) (cm-1): 2981 and 2932
(νC–H, aliphatic), 1613 (νC=O, carbonyl), 1132 (νC–F, trifluoromethyl), 758 (γC–H, pyridine). Anal. Calcd.
for C66H48Cu2F12N4O8S2: C, 54.88; H, 3.35; N, 3.88; O, 8.86; S, 4.44%. Found: C, 54.76; H, 3.28; N,
S4

3.69; O, 8.77; S, 4.32%. TGA analysis: the first stage of weight loss occurred at 105 °C corresponding
to the loss of two solvent benzene molecules (10.8 %). The second stage at 210 °C was corresponding to
the loss of coordinated pyridine units (10.9 %). The main structure decomposed at 461 °C.
10. Co2Py4L2 (12).
2
Orange, plate crystals were obtained through the same way as that of 9, yield: 18 mg (42 %). IR (KBr)
(cm-1): 2982 and 2931 (νC–H, aliphatic), 1621 (νC=O, carbonyl), 1136 (νC–F, trifluoromethyl), 755 and
701 (γC–H, pyridine). Anal. Calcd. for C64H46Co2F12N6O8S2: C, 53.49; H, 3.23; N, 5.85; O, 8.91; S,
4.46%. Found: C, 53.38; H, 3.31; N, 5.80; O, 8.85; S, 4.41%. TGA analysis: the first weight loss
occurred at 220 °C corresponding to the loss of coordinated pyridine molecules (21.9 %). The main
structure decomposed at 415 °C.
Scheme S1. The keto-enol tautomerisation of H2L1.
O
O
O
O
OH O
O
OH
S
N
S
N
enol-form
keto-form
Part 2 Crystal Structure Determinations
The molecular structures of 7, 1, 8, 9, 10, 11 and 12 were shown in Figures S1-S7. The unit cell, data
collection and refinement parameters are located in the following Tables S1-S2. Table S3-S6 show
selected bond lengths and angles of H2L1, 1, 7, 8.
Type I – four coordination. The structure of this type appears only in [Cu2L1 ]·2DMF (5). 5
2
crystallizes in the monoclinic space group P21/c. Each Cu(II) center has a square planar coordinated
sphere surrounded by four oxygen atoms from two β-diketonato fragments. This kind of structure has
been described by us before.1
Type II – five coordination. In Figure S1a, an infinite 1D columnar arrangement along a-axis has
been found, which was stabilized by the hydrogen bonding interactions formed between O atoms of the
ligand and H(C) atoms of solvent THF molecule[d(O2···H29B(C29)) = 2.710 Å, d(O2···C29) = 3.596 Å,
∠(C29–H29B···O2) = 152.08°]; [d(O5···H28B(C28)) = 2.716 Å, d(O5···C28) = 3.348 Å, ∠(C28–
H28B···O5) = 123.23°]. The 1D structure also incorporates 1D channels down a-axis (Figure S1a, inset).
1D columns are linked each other through edge-to-face π-π stacking interactions to form a 3D
framework [the centroid-centroid separation is 4.553 Å; the ring planes intersect at an angle of 11.36°]2
(Figure S1b).
S5

(a)
(b)
Figure S1. (a) View showing the 1D column along the a-axis of complex 7. Inset: showing 1D channels. (b) 1D
columns interacted with each other through edge-to-face π-π interactions to generate a 3D structure (Black balls
represent the centroids of benzene rings).
Type III – six coordination. Different from 3, complex molecules of 1 interact with each other
through H-bondings formed between O atoms of the ligand and H(C) atoms of the pyridine rings to
form 1D columns down b-axis [d(O3···H35(C35)) = 2.670 Å, d(O3···C35) = 3.285 Å, ∠(C35–H35···O3)
= 124.35°] (Figure S2b). The 1D structure also incorporates 1D channels down b-axis. As the same as
that of 7, 1D columns linked to each other through edge-to-face π-π stacking interactions to be a 3D
framework [the centroid−centroid separations is 4.279 Å; the ring planes intersect at an angle of 21.40°].
(a)
S6

(b)
Figure S2. (a) The ORTEP structure of [Zn2Py4L1 ]·2Py (1) (50% thermal ellipsoid probability). (b) View showing the
2
1D column along the b-axis. All hydrogen atoms are omitted for clarity.
Figure S3. The ORTEP structure of 8 (50% thermal ellipsoid probability). All hydrogen atoms and solvents molecules
are omitted for clarity.
Figure S4. The ORTEP structure of 9 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
S7

Figure S5. The ORTEP structure of 10 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
Figure S6. The ORTEP structure of 11 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
Figure S7. The ORTEP structure of 12 (50% thermal ellipsoid probability). All hydrogen atoms are omitted for clarity.
S8

Table S1. Crystal data and structure refinement parameters for the compounds H2L1, 1, 7 and 8.
H2L1
1
7
8
CCDC
formula
fw
cryst system
Space group
a/Å
b/Å
c/Å
a/º
β/º
298940
C32H25NO4S
519.59
Monoclinic
P21/c
15.276(5)
16.211(5)
10.466(3)
660612
C94H76N8O8S2Zn2
1636.38
Triclinic
Pī
11.092(5)
12.371(5)
15.530(5)
100.918(5)
105.277(5)
95.784(5)
936.8(7)
2
1.103
684
293(2)
0.71073
2.36, 21.10
7789, 515
0.0577
0.1410
0.925
673738
C62H52F12N4O10S2Zn2
1435.94
Triclinic
Pī
8.925(7)
9.851(7)
19.046(13)
88.040(11)
83.163(12)
64.338(9)
1498.3(19)
1
1.585
728
293(2)
0.71073
2.15, 25.05
5239, 416
0.0766
0.1662
0.999
711281
C64H46Cd2F12N6O8S2
1543.99
Triclinic
Pī
8.896(5)
10.216(5)
18.837(5)
92.476(5)
99.680(5)
113.835(5)
1531.9(12)
2
2.910
1235
298(2)
0.71073
1.10, 25.00
5367, 425
0.0579
0.0841
1.087
98.021(4)
γ/º
V /Å3
2566.4(13)
4
1.345
Z
Dc/g cm-3
F(000)
T/K
1088
293(2)
0.71073
1.84, 25.10
4485, 343
0.0487
0.1096
1.022
λ/Å
θmin-max /º
Nref, Npar
R [I>2σ(I)]
R (all data)
GOF on F2
Table S2. Crystal data and structure refinement parameters for 9-12.
9
10
12
11
CCDC
formula
fw
cryst Syst
Space group
a / Å
b / Å
c / Å
α / º
β / º
660613
C64H46Ni2F12N6O8S2
1436.58
Triclinic
Pī
8.675(5)
9.988(5)
19.371(5)
89.890(5)
83.436(5)
66.425(5)
1526.5(12)
2
673759
700927
700930
C64H46Mn2F12N6O8S2
1429.07
Triclinic
Pī
8.544(6)
9.937(7)
19.474(13)
91.086(8)
96.614(9)
111.179(8)
1528.2(17)
2
C66H48Cu2F12N4O8S2
1444.28
Triclinic
Pī
9.3769(2)
9.9380(2)
19.0906(4)
86.1590(10)
82.3120(10)
63.4480(10)
1577.02(6)
1
C64H46Co2F12N6O8S2
1437.05
Triclinic
Pī
8.7278(14)
10.0793(15)
19.420(3)
89.497(11)
83.290(11)
66.211(11)
1551.2(4)
1
γ / º
V / Å3
Z
Dc / g cm-3
F(000)
T (K)
1.391
648
298(2)
1.553
726
298(2)
1.521
734
296(2)
1.538
730
296(2)
0.71069
2.12,26.06
5979,483
0.048
0.0877
1.097
0.71073
2.11,25.00
5231,368
0.1472
0.1822
0.996
0.71073
2.29, 24.74
7213,425
0.0543
0.0726
1.037
0.71073
2.41,24.99
7108, 425
0.0569
0.1065
1.039
λ / Å
θmin-max / º
Nref, Npar
R (I>2σ(I))
R (all data)
GOF
S9

Table S3. Selected bond lengths [Å] and angles [º] for H2L1.
Bond
C5−C7
C7−O1
C7−C8
C8−C9
lengths
Bond
O1−C7−C8
C8−C7−C5
C9−C8−C7
O2−C9−C8
O2−C9−C10
C8−C9−C10
O3−C22−C23
O3−C22−C19
C23−C22−C19
C24−C23−C22
O4−C24−C23
C23−C24−C25
angles
1.470(5)
1.289(5)
1.403(5)
1.393(6)
1.276(5)
1.504(4)
1.281(4)
1.410(5)
1.498(4)
1.379(5)
1.304(4)
1.476(4)
121.2(4)
121.7(4)
119.8(4)
120.8(4)
117.3(4)
121.9(4)
120.1(4)
117.2(3)
122.7(3)
120.8(4)
120.7(4)
124.3(3)
C9−O2
C9−C10
C22−O3
C22−C23
C22−C19
C23−C24
C24−O4
C24−C25
Table S4. Selected bond lengths [Å] and angles [º] for complex 7.
Bond lengths
Bond angles
129.0(7)
O5−C2−C3
2.001(4)
1.989(5)
1.990(5)
2.004(5)
1.498(11)
1.245(7)
1.335(9)
1.379(9)
1.241(7)
1.471(8)
1.460(9)
1.247(7)
1.405(9)
1.320(9)
1.242(7)
O2−Zn1
O3−Zn1
O4−Zn1
O5−Zn1
C1−C2
C2−O5
C2−C3
C3−C4
C4−O2
117.7(7)
124.9(6)
123.1(6)
121.1(6)
121.7(6)
120.5(6)
123.9(6)
130.9(7)
117.2(7)
87.9(2)
C3−C2−C1
C2−C3−C4
O2−C4−C3
C3−C4−C5
O3−C19−C20
C20−C19−C18
C21−C20−C19
O4−C21−C20
C20−C21−C22
O3−Zn1−O4
O3−Zn1−O2
O2−Zn1−O5
O3−Zn1−O5
O4−Zn1−O5
C4−C5
C18−C19
C19−O3
C19−C20
C20−C21
C21−O4
84.15(19)
87.77(19)
158.6(2)
91.0(2)
S10

Table S5. Selected bond lengths [Å] and angles [º] for complex 1.
Bond
lengths
Bond
angles
2.047(2)
2.060(3)
2.066(3)
2.069(2)
1.271(4)
1.274(4)
1.274(4)
1.264(4)
1.502(5)
1.400(5)
1.404(5)
1.500(5)
1.507(5)
1.405(5)
1.410(5)
1.510(5)
88.91(10)
87.05(10)
87.36(10)
96.74(10)
128.3(2)
128.3(2)
128.2(2)
124.7(4)
126.0(4)
125.5(4)
119.6(3)
128.3(2)
129.3(2)
124.7(3)
119.4(4)
119.5(3)
Zn1−O2
Zn1−O3
Zn1−O1
Zn1−O4
O3−C9
O4−C11
O1−C26
O2−C24
C8−C9
C10−C9
C10−C11
C12−C11
C22−C24
C25−C26
C25−C24
C27−C26
O2−Zn1−O3
O2−Zn1−O1
O3−Zn1−O4
O1−Zn1−O4
C9−O3−Zn1
C11−O4−Zn1
C26−O1−Zn1
C26−C25−C24
C9−C10−C11
O1−C26−C25
C25−C26−C27
C9−O3−Zn1
C24−O2−Zn1
O4−C11−C10
C10−C11−C12
C10−C9−C8
Table S6. Selected bond lengths [Å] and angles [º] for complex 8.
Bond
Cd1−O1
Cd1−O2
Cd1−O3
Cd1−O4
Cd1−N2
Cd1−N3
C2−C1
C3−C2
C3−C4
C5−C4
O1−C2
lengths
Bond
O1−Cd1−O3
O1−Cd1−O4
O3−Cd1−O4
O1−Cd1−O2
O3−Cd1−O2
O4−Cd1−O2
O1−Cd1−N3
O3−Cd1−N3
O4−Cd1−N3
O2−Cd1−N3
O1−Cd1−N(2)
O3−Cd1−N2
O4−Cd1−N2
O2−Cd1−N2
N3−Cd1−N2
C2−C3−C4
angles
2.221(5)
2.273(4)
2.234(4)
2.257(5)
2.380(6)
2.291(6)
1.479(3)
1.380(9)
1.393(9)
1.491(9)
1.245(8)
1.264(7)
1.252(7)
1.247(7)
1.459(9)
1.425(9)
1.352(9)
170.06(16)
108.29(17)
81.64(16)
81.51(17)
88.55(16)
169.25(16)
89.61(19)
90.94(19)
89.75(18)
94.83(18)
82.51(19)
98.21(19)
85.16(18)
91.93(19)
168.76(19)
126.9(6)
O2−C4
O3−C17
O4−C19
C16−C17
C18−C17
C18−C19
127.4(6)
C19−C18−C17
S11

Part 3
acetonitrile
benzene
acetonitrile
benzene
1.0
1.0
0.8
0.6
0.4
0.2
0.0
CHCl
3
CHCl
3
0.8
0.6
0.4
0.2
0.0
DMF
hexane
THF
DM F
hexane
THF
400
500
600
700
800
300
400
500
600
λ/nm
λ/nm
Figure S8. Linear absorption (left) and OPEF (right) spectra of H2L1 in six solvents, c = 10 µM.
1.0
0.5
0.0
1.0
0.5
0.0
acetonitrile
benzene
acetonitrile
benzene
CHCl
3
CHCl
3
DMF
hexane
THF
DM F
hexane
THF
300
400
500
600
500
600
700
λ/nm
λ/nm
Figure S9. Linear absorption (left) and OPEF (right) spectra of H2L2 in six solvents, c = 10 µM.
acetonitrile
acetonitrile
1.00
benzene
1.00
benzene
CHCl
3
CHCl
3
0.75
DMF
DMF
hexane
THF
0.75
0.50
0.25
0.00
hexane
THF
0.50
0.25
0.00
300
400
500
600
500
600
700
λ/nm
λ/nm
Figure S10. Linear absorption (left) and OPEF (right) spectra of H2L1 in six solvents, c = 1.0 µM.
S12

LUMO
HOMO
Figure S11. Spatial plots of the selected frontier molecular orbitals of the enol form of (L2)2−. The time−dependent
hybrid density functional theory (TDDFT) calculations were performed using B3LYP /6-31G*//6-31G**.
H L2
1.0
2
H L
2
4000
3000
2000
1000
0
2
2
(L2)2-
7
(L )2-
0.8
0.6
0.4
0.2
0.0
7
8
8
9
9
10
11
12
10
11
12
500
700
λ/nm
λ/nm 600
300
400
500
600
Figure S12. Linear absorption (left) and OPEF (right) spectra of H2L2, (L2)2− and its complexes in THF, c = 10 µM.
S13

Table S7. Photophysical data of all the compounds.
TP
Compd
Solvent
λab (nm)
335, 419
342, 434
339, 434
341, 433
338, 438
350, 415
ε (× 104 dm3 mol−1 cm−1)
λem (nm)
529
aλem
bφ
cτ
dδmax
H2L1
Hexane
Benzene
CHCl3
THF
556
572
3.6, 2.1
465, 563
457, 565
534
570
0.38
6.29
155
CH3CN
DMF
solid
621
e Cal.
enol
336, 446
402
499
677
508
541
538
0.71
0.22
0.35
0.32
0.27
790
6031
21
keto
(L1)2-
THF
342, 428
342, 412
344, 418
342, 422
345, 425
341, 431
341, 428
3.8, 2.3
6.8, 5.6
6.9, 4.5
6.0, 4.4
5.9, 4.2
4.8, 3.5
8.0, 6.8
561
544
562
543
543
544
545
7.05
5.83
6.20
THF
568
664
1
THF
2
THF
3
THF
4
5
THF
THF
6
H2L2
Hexane
Benzene
CHCl3
THF
334, 491
325, 492
316, 423
322, 434
318, 420
317, 414
543
582
560
536
547
545
632
2.6, 1.1
547
0.46
7.03
204
CH3CN
DMF
solid
Cal.
(L2)2-
7
enol
338, 462
319, 402
318, 419
320,417
320,419
321,417
321,417
317,416
528
598
560
557
0.36
0.51
0.32
0.30
812
28
THF
2.8, 1.2
7.0, 2.9
7.4, 3.2
6.7, 2.8
4.5, 3.0
5.8, 2.9
5.6, 2.4
538
553
550
537
537
538
535
4.32
7.37
7.45
THF
369
366
8
THF
THF
9
THF
10
11
12
THF
THF
a
b
c
d
Peak position of TPEF in nm. The fluorescence quantum yield. Fluorescence lifetime in ns. TPA
cross-section in GM. e Calculated results.
S14

Part 4
The emission intensity of H2L1, H2L2, 1, 2, 7 and 8 investigated at 780 nm were shown in Figure S13.
The linear dependence on the square of input laser power suggests that it is obviously a two-photon
excitation mechanism.
4.4
4.2
4.0
3.8
3.6
3.4
3.2
3.0
5.2
4.8
4.4
4.0
H2L1
complex 1
Slope = 1.97
Slope = 1.97
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
1.6
1.8
2.0
2.2
Log I
in
Log I
in
5.6
5.2
4.8
4.4
4.0
3.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
3.0
complex 2
H L2
2
Slope = 2.01
Slope = 1.97
1.4
1.6
1.8
2.0
2.2
2.4
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
Log I
in
Log I
in
4.8
4.4
4.0
3.6
3.2
4.4
4.0
3.6
3.2
complex 7
complex 8
Slope = 1.98
Slope = 2.00
1.6
1.8
2.0
2.2
1.6
1.8
2.0
2.2
Log I
Log I
in
in
Figure S13. Log–Log linear of squared dependence of induced fluorescence signal and incident irradiance intensity of
two ligands and complexes 1, 2, 7 and 8.
S15

Part 5
Table S8. Cell viability (%) of HeLa cells after incubation for 24 h with different concentration of the chromophores.
Concentration (µM)
Compd./viability(%)
10
20
50
100
H2L1
H2L2
1
99.46 5.95
97.50 1.78
95.16 3.25
96.49 3.23
95.57 3.48
91.58 3.49
87.62 2.65
90.20 3.99
79.18 3.46
78.24 2.66
75.81 3.17
75.43 2.79
65.11 2.06
55.38 5.33
64.42 5.7
58 2.03
7
Figure S14 The variable temperature 1H NMR of Zn2Py2L2
2
S16

Figure S15 MALDI-TOF Mass spectrometry of 7
References
(1) Li, D. M.; Zhou, W.; Xu, G. Y.; Zhou, H. P.; Wu, J. Y.; Tian, Y. P.; Tao, X. T.; Jiang, M. H. J. Mol. Struct. 2009,
929, 120.
(2) Quan, R. W.; Li, Z.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 8156.
S17