Supporting Information
© Wiley-VCH 2007
69451 Weinheim, Germany
Metal-tunable Nanocages worked as Artificial Chemosensors
Cheng He, Zhihua Lin, Zheng He, Chunying Duan,* Chunhu Xu, Zheming Wang and Chunhua Yan*
Contents
1． Experimental Section.
2． Figure S1 Electrospray mass spectrum of 1.
3． Figure S2 Uv-vis spectra of the free ligand H3L1 upon the addition of Co(ClO4)2⋅6H2O.
4． Equations for the association constant calculation of the 1:1 complexation.
5． Figure S3 Uv-vis titration of compound 1 upon the addition of glucosamine and the linear fitting of the
titration curve.
6． Figure S4 Uv-vis titration of compound 2 upon the addition of glucosamine and the linear fitting of the
titration curve.
7． Figure S5 ESI of compound 1 in DMSO/CH3OH in the presence of glucosamine.
8． Figure S6 ESI-MS of compound 2 in DMSO/CH3OH.
9． Figure S7 Fluorescent titration of H3L1 upon addition of Zn(ClO4)2⋅6H2O.
10． Figure S8 1H NMR spectra of compound 2 in the presence of equimolar glucosamine in d6-DMSO.
11． Figure S9 Solid state emission spectra of compounds 4 and 5。
12． Figure S10 Molecular structure of 1.
13． Figure S11 Molecular structure of 2.
14． Figure S12 Molecular structure of 3.
15． Figure S13 Molecular structure of 4.
16． Figure S14 Molecular structure of 5.
17． Figure S15 The packing of the cages in compound 5
18． Table S1. Selected bond lengths (Å) and angles (°) of compound 1.
19． Table S2. Selected bond lengths (Å) and angles (°) of compound 2.
20． Table S3. Selected bond lengths (Å) and angles (°) of compound 3.
21． Table S4. Selected bond lengths (Å) and angles (°) of compound 4.
22． Table S5. Selected bond lengths (Å) and angles (°) of compound 5.
1. Experimental Section.
1.1 Materials and Methods. All chemicals were of reagent grade quality obtained from commercial sources and
used without further purification. The elemental analyses of C, H and N were performed on a Vario EL III
elemental analyzer. 1H NMR and 13C NMR spectra were measured on a Varian INOVA 400M spectrometer. API
mass spectra were recorded on HP1100LC/MSD spectrometer. ESI mass spectra were carried out on a
HPLC-Q-Tof MS spectrometer using methanol as mobile phase. Uv-vis spectra were measured on a HP 8453
spectrometer. The solution fluorescent spectra were measured on JASCO FP-6500. Both excitation and emission
slit widths were 5 nm. The solid state fluorescent spectra were measured on Hitachi F-4500, the excitation slit
width was 10nm and emission slit width was 5 nm, respectively.
1.2 Preparation
1,3,5-benzene-tricarbohydrazide: A mixture solution of
hydrazine hydrate (80%) (30mmol, 1.877g) and
trimethyl-1,3,5-benzene-tricarboxylate (2mmol, 0.504g) in methanol (50mL) was stirred over 12h. The white
precipitate formed, was collected by filtration, washed with methanol and dried in vacuum. Yield: 0.45g, (89%).
H3L1: 1,3,5-Benzene-tricarbohydrazide (1 mmol, 0.252g) was added to a EtOH solution (70 mL) containing
2-quinoline-carbaldehyde (3.3 mmol, 0.52 g). After 5 drops of acetic acid was added, the yellow mixture was
heated at boiling temperature under magnetic stirring for 24h. During the reaction, pale yellow precipitate was
formed, which was collected by filtration, and recrystallized from a mixture of CH3OH/CHCl3 (v:v=1:4). Yield:
0.54g (72%). Anal calc. for H3L C39H27N9O3· CH3OH·2H2O: C, 65.12; H, 4.78; N, 17.09%. Found: C 65.50, H 4.62,
N 16.86%. 1H NMR (DMSO-d6, ppm): 12.70(br, 3HNH), 8.91(s, 3H7), 8.82(s, 3H8), 8.72(d, 3H1, J = 13.6Hz),
8.49(d, 3H6, J = 12.4Hz), 8.23(t, 3H2, J = 6.8Hz), 8.05(d, 3H3, J = 8.4Hz), 7.82(br, 3H5), 7.67(t, 3H4, J = 7.4Hz).
API-MS m/z: 670.3 ([M-H+]), 692.3 ([M-Na+]).
H3L2: 1,3,5-Benzene-tricarbohydrazide (1 mmol, 0.252g) was added to a CH3OH solution (70 mL) containing
2-pyridinecarboxaldehyde (3.3 mmol, 0.353 g). After 5 drops of acetic acid was added, the mixture was heated at
boiling temperature under magnetic stirring for 10h. During the reaction, a white precipitate was formed, which
was collected by filtration, washed with CH3OH, and dried in vacuo. Yield: 0.43g (77%). Anal calc. for
C27H21N9O3·2H2O: C, 58.37; H, 4.54, N, 22.69%. Found C, 58.81; H, 4.59, N, 23.07%. 1H NMR (DMSO-d6, ppm):
12.43 (s, 3HNH), 8.71 (s, 3H4), 8.65 (d, 3H9), 8.55 (s, 3H1), 8.04 (d, 3H6, J = 7.2Hz), 7.93 (t, 3H7, J = 14.8Hz), 7.47
(t, 3H8, J = 11.6Hz).
13
C NMR (100 MHz, d6-DMSO, ppm): 162.08(C3), 152.94(C5), 149.48(C9), 148.77(C4),
136.91(C7), 133.94(C2), 130.09(C1), 124.53(C8), 120.08(C6). API-MS m/z: 520.2 ([M-H+]), 542.1 ([M-Na+]).
6
N
N
NH
O
O
8
HN
5
4
3
N
N
H
N
N
N
2
7
9
NH
O
1
1
O
2
3
8
N
N
H
N
4
5
7
6
O
HN
N
O
N
N
N
H3L1
H3L2
Compound 1: A solution of Co(ClO4)2·6H2O (0.028g, 0.075mmol) in methanol (6 mL)was layered onto a solution
of H3L1 ligand (0.034g, 0.05mmol) in CH3OH/CHCl3 (v:v = 1:4, 6mL). The solution was left for one week at room
temperature to give X-ray quality red block crystals. Yield: about 75% (based on the crystals that have been
collected and then dried in vacuum).
Compound 2: A solution of Zn(ClO4)2·6H2O (0.028g, 0.075mmol) in methanol (6 mL)was layered onto a solution
of H3L1 ligand (0.034g, 0.05mmol) in CH3OH/CHCl3 (v:v = 1:4, 6mL). The solution was left for one week at room
temperature to give X-ray quality yellow block crystals. Yield: about 75% (based on the crystals that have been
collected and then dried in vacuum). 1H NMR (DMSO-d6, ppm): 12.68(br, HNH), 8.88(s, H7), 8.78(s, H8), 8.53(br,
H1), 8.22(d, H6, J = 12.4Hz), 8.13(br, H2), 8.07(d, H3, J = 8.4Hz), 7.86(br, H5), 7.70(t, H4, J=6.4Hz).
Compound 3: A solution of Ni(BF4)2·6H2O (0.026g, 0.075mmol) in methanol (6 mL)was layered onto a solution
of H3L1 ligand (0.026g, 0.05mmol) in CH3OH/CHCl3 (v:v = 1:4, 6mL). The solution was left for two weeks at
room temperature to give X-ray quality brown block crystals. Yield: about 50% (based on the crystals that have
been collected and then dried in vacuum).
Compound 4: A solution of Eu(NO3)3·6H2O (0.034g, 0.075mmol) in methanol (6 mL) was layered onto a solution
of H3L1 ligand (0.026g, 0.05mmol) in CH3OH/CHCl3 (v:v = 1:4, 6mL). The solution was left for one week at room
temperature to give X-ray quality yellow block crystals. Yield: about 60% (based on the crystals that have been
collected and then dried in vacuum).
Compound 5: A solution of Tb(NO3)3·6H2O (0.034g, 0.075mmol) in methanol (6 mL) was layered onto a solution
of H3L1 ligand (0.026g, 0.05mmol) in CH3OH/CHCl3 (v:v = 1:4, 6mL). The solution was left for one week at room
temperature to give X-ray quality yellow block crystals. Yield: about 65% (based on the crystals that have been
collected and then dried in vacuum).
Crystallography
X-Ray intensity data were measured at 180(2) K on a Bruker SMART APEX CCD-based diffractometer (Mo–Kα
radiation, λ = 0.71073 Å) using the SMART and SAINT programs. Raw data frame integration and Lp corrections
were performed with SAINT+. Final unit cell parameters were determined by least-squares refinement of strong
reflections for the respective compounds 1–5. The structures were solved by direct methods and refined on F2 by
full-matrix least-squares methods with SHELXTL version 5.1. All of the non-hydrogen atoms except the disordered
solvent molecules and anions were refined with anisotropic thermal displacement coefficients. Hydrogen atoms of
organic ligands were located geometrically and refined in a riding model, whereas those of solvent molecules were
not treated during the structural refinements. To assist the refinements, several restraints were applied: (1) the
geometrical constraints of idealized regular polygons and polyhedrons for the anions were used; (2) thermal
parameters on adjacent atoms in disordered moieties were restrained to be similar. CCDC 656404- 656408 contain
the supplementary crystallo-graphic data. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/
retrieving.html (or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB12EZ, UK;
fax: (+44) 1223-336-033; or [email protected]).
For compound 1, of the four teams of perchlorate anions were found, two of the chlorine atom were partly
occupied with the site occupancy factor (s.o.f.) being fixed at 0.91667 and 0.08333 for Cl(3) and Cl(5), respectively.
The oxygen atoms of these anions were also disordered with the s.o.f. of them being determined through free
variables, except the oxygen atoms O(51) and O(52), the s.o.f. was fixed at 0.08333 and 0.25, respectively. Except
those of solvent molecules, the hydrogen atoms were located geometrically and refined in a riding model. For
compound 2, five teams of perchlorate anions were found, and four of the chlorine atom were partly occupied with
the site occupancy factor (s.o.f.) being fixed at 0.83333 for Cl(2), and Cl(3), 0.16667 for Cl(4) and Cl(5),
respectively. For compound 3, two teams of tetrafluorobroate anions were found, of one of the anion were partly
occupied with the s.o.f being fixed at 0.50, and the other one is full occupied with the s.o.f. of the disordered
fluorine atoms being refined as free variables. For compound 4, eight teams of nitrate anions were found. Of the
four anions acted as terminal coordinated chelators, the oxygen atoms in one anion were disordered with the s.o.f.
of the oxygen atoms within the two disordered parts were fixed at 0.75 and 0.25, respectively. Of the teams of free
anions, one was partly occupied with the s.o.f. of the atoms being foxed at 0.50, two of them were situated at
special positions with the s.o.f of the partly occupied nitrogen atom being fixed at 0.16667 and the s.o.f. of the
disordered oxygen atoms attached being fixed at 0.50, respectively. For compound 5，seven teams of anions were
found. Of the four anions acted as terminal coordinated chelators, three of them were refined partly occupied with
the s.o.f. for these atoms being fixed at 0.66667. Of the three teams of free anions, one was partly occupied with the
s.o.f. of the atoms being foxed at 0.66667, one was situated at special positions. Several teams of chloroform,
methanol molecules and water molecules were found heavy disordered. The s.o.f. of these atoms were fixed
directly and gave the final molecular formula of these compounds.
2. Figure S1 ESI-MS of compound 1 in CH3OH with the calculated and observed isotopic patterns for 1007.54 and
1040.88 being exhibited.
Theoretical
Experimental
1007.54:
[Co6H3L14]3+
1040.88:
[Co6H4L14(ClO4)]3+
1074.57:
[Co6H5L14(ClO4)2]3+
1141.33:
[Co6H7L14(ClO4)4]3+
1230.61:
[Co6H3L15]3+
1264.30:
[Co6H4L15(ClO4)]3+
3. Figure S2 The family of the Uv-vis spectra of the free ligand H3L1 (1.0×10-5 M) upon the addition of a standard
Absorbance
solution of Co(ClO4)2⋅6H2O.
0.4
0.2
0.0
300
400
500
Wavelength (nm)
600
4. Association Constant Calculation:
Generally, for the formation of 1: 1 complexation species formed by the cage compound and the guest anion (G), if
we assume xC0 to the concentration of complexes species cage-NG, when the concentration of the added guest
anion is a nC0 with the original concentration of the cage being fixed at C0:
cage
cage only
cage - G
G
C0
nC0 G is added
K=
+
(n-x)C0
(1-x)C0
[cage-G]
xC0
(1)
[cage][G]
The measurements are performed under the conditions where the absorbance value of the free cage compound in
such a concentration is A0; after addition of a given amount (nC0) of G, the fluorescent intensity becomes:
A = A1 x + A0 (1-x)
(2)
where Al is the absorbance of the saturated value in the presence of excess guest anions.
It is easy to derive the usual equation:
A-A0
Al-A0
= x
(3)
From eqs (1) and (3), we can obtain the equation:
n
A-A0
=
1
KC0
Ks can be obtained by a linear analysis of (X)
1
Al-A
1
Al - A
+
1
Al-A0
(4)
n
versus (Y).
A-A 0
5. Figure S3 Uv-vis titration of compound 1 (5×10-6 M acetonitrile solution) upon the addition of the standard
solution containing glucosamine (top picture) and the linear fitting of the titration data using the equation
mentioned above (bottom picture).
0.6
0.4
0.2
0.0
300
400
500
600
Wavelength (nm)
14
R=0.99
12
n
A-A 0
Y
Absorbance (A)
0.8
10
8
4
6
8
X1
Al-A
10
12
6. Figure S4 Uv-vis titration of compound 2 (5×10-6 M acetonitrile solution) upon the addition of the standard
solution glucosamine (top picture) and the linear fitting of the titration data using the equation mentioned above
(bottom picture).
Absorbance (A)
1.0
0.8
0.6
0.4
0.2
0.0
300
400
500
600
Wavelength (nm)
12
R=0.99
n10
A-A 0
8
1.5
2.0
2.5
X
n
A-A 0
7. Figure S5 ESI-MS of compound 1 in DMSO/CH3OH in the presence of glucosamine with the calculated and
observed isotopic patterns for the 800.65 [Co6(H4L14)(NH2-Glu)]4+ and 1067.13 [Co6(H3L14)(NH2-Glu)]3+ being
exhibited.
Theoretical
Experimental
8. Figure S6 ESI-MS of compound 2 in DMSO/CH3OH.
652.52:
[Zn6H7L14(ClO4)2]5+
672.91:
[Zn6H8L14(ClO4)3]5+
692.91:
[Zn6H9L14(ClO4)4]5+
840.89:
[Zn6H7L14(ClO4)3]4+
865.89:
[Zn6H8L14(ClO4)4]4+
1120.87:
[Zn6H6L14(ClO4)3]3+
1154.50:
[Zn6H7L14(ClO4)4]3+
1187.51:
[Zn6H8L14(ClO4)5]3+
1221.13:
[Zn6H9L14(ClO4)6]3+
1254.81:
[Zn6H10L14(ClO4)7]3+
9. Figure S7 Fluorescent titration of H3L1 (1.0×10-5 M acetonitrile solution, excited at 380nm) upon the addition of
a standard solution of Zn(ClO4)2⋅6H2O.
Intensity
15
10
5
1
H3L
0
500
600
Wavelength (nm)
700
10 Figure S8 1H NMR spectra of compound 2 in the presence of equimolar glucosamine in d6-DMSO.
11. Figure S9 Solid state emission spectra of compounds 4 (left picture excitation at 315 nm) and compound 5
(right picture excitation at 303 nm)
2
5
D0
7
FJ
1
J=0
3
600
650
Wavelength (nm)
4
700
300
400
500
600
Wavelength (nm)
700
800
12. Figure S10 Molecular structure of 1.
13. Figure S11 Molecular structure of 2.
14. Figure S12 Molecular structure of 3.
15. Figure S13 Molecular structure of 4.
16. Figure S14 Molecular structure of 5.
17. Figure S15 The packing of the cages in compound 5 with 1D channels along the c-direction (the
radii the channels is about 1.5nm)
18. Table S1. Selected bond lengths (Å) and angles (°) of compound 1.
Co1-N8
2.036(3)
Co1-N5A
2.045(4)
Co1-O3
2.115(3)
Co1-N7
2.173(3)
Co1-O2A
2.177(3)
Co1-N4A
2.194(3)
Co2-N2
2.030(3)
Co2-N11
2.038(3)
Co2-O4
2.114(3)
Co2-O1
2.118(3)
Co2-N1
2.157(3)
Co2-N10
2.160(4)
O1-C11
1.254(5)
O2-C24
1.244(5)
O2-Co1B
2.177(3)
O3-C37
1.264(5)
O4-C50
1.259(5)
N1-C9
1.303(5)
N1-C1
1.355(6)
N2-C10
1.269(5)
N2-N3
1.390(5)
N3-C11
1.362(5)
N4-C14
1.375(5)
N4-C22
1.307(6)
N5-C23
1.247(5)
N4-Co1B
2.194(3)
N5-Co1B
2.045(4)
N5-N6
1.358(4)
N7-C35
1.340(5)
N6-C24
1.354(6)
N8-C36
1.270(6)
N7-C27
1.364(5)
N9-C37
1.326(5)
N8-N9
1.361(4)
N10-C40
1.380(6)
N10-C48
1.327(5)
N11-N12
1.346(5)
N11-C49
1.269(6)
C1-C2
1.408(7)
N12-C50
1.347(5)
C2-C3
1.383(9)
C1-C6
1.417(7)
C4-C5
1.344(9)
C3-C4
1.505(9)
C6-C7
1.355(7)
C5-C6
1.423(8)
C8-C9
1.394(6)
C7-C8
1.339(7)
C11-C12
1.485(6)
C9-C10
1.457(6)
C12-C13
1.377(5)
C12-C39
1.377(6)
C14-C19
1.418(6)
C13-C25
1.390(6)
C15-C16
1.323(6)
C14-C15
1.423(7)
C17-C18
1.334(8)
C16-C17
1.420(8)
C19-C20
1.395(7)
C18-C19
1.399(6)
C21-C22
1.397(6)
C20-C21
1.332(6)
C24-C25
1.461(6)
C22-C23
1.489(5)
C26-C38
1.387(5)
C25-C26
1.398(6)
C27-C32
1.437(7)
C27-C28
1.405(6)
C29-C30
1.378(7)
C28-C29
1.355(6)
C31-C32
1.412(7)
C30-C31
1.382(7)
C33-C34
1.349(7)
C32-C33
1.391(7)
C35-C36
1.484(6)
C34-C35
1.390(7)
C38-C39
1.381(6)
C37-C38
1.505(6)
C40-C45
1.425(7)
C40-C41
1.396(6)
C42-C43
1.413(9)
C41-C42
1.371(8)
C44-C45
1.430(8)
C43-C44
1.351(8)
C46-C47
1.352(8)
C45-C46
1.375(7)
C48-C49
1.451(7)
C47-C48
1.414(7)
C51-C52
1.364(5)
C50-C51
1.495(7)
C52-C51B
1.396(6)
C51-C52A
1.396(6)
N8-Co1-N5A
158.0(1)
N8-Co1-O3
74.0(1)
N5A-Co1-O3
94.1(1)
N8-Co1-N7
76.1(1)
N5A-Co1-N7
118.2 (1)
O3-Co1-N7
147.6(1)
N8-Co1-O2A
87.5(1)
N5A-Co1-O2A
74.3(1)
O3-Co1-O2A
92.3(1)
N7-Co1-O2A
98.9(1)
N8-Co1-N4A
123.1(1)
N5A-Co1-N4A
74.4(1)
O3-Co1-N4A
90.2(1)
N7-Co1-N4A
95.6(1)
148.6(1)
N2-Co2-N11
160.1(2)
N2-Co2-O4
89.8(1)
N11-Co2-O4
75.0(1)
N2-Co2-O1
75.5(1)
N11-Co2-O1
92.4(1)
O4-Co2-O1
93.8(1)
N2-Co2-N1
75.2(1)
N11-Co2-N1
117.6(1)
O4-Co2-N1
92.6(1)
O1-Co2-N1
150.0(1)
N2-Co2-N10
120.3(2)
N11-Co2-N10
75.7(1)
O4-Co2-N10
150.0(1)
O1-Co2-N10
93.9(1)
N1-Co2-N10
95.2(1)
C11-O1-Co2
113.8(3)
O2A-Co1-N4A
Symmetry codes: A. -y+1, x-y, z
B. -x+y+1, -x+1, z
19. Table S2. Selected bond lengths (Å) and angles (°) of compound 2.
Zn1-N5
2.040(4)
Zn1-N11
2.057(4)
Zn1-N4
2.143(4)
Zn1-N10
2.145(4)
Zn1-O2
2.193(3)
Zn1-O4
2.195(4)
Zn2-N8A
2.044(4)
Zn2-N2
2.053(4)
Zn2-N7A
2.156(4)
Zn2-N1
2.173(3)
Zn2-O3A
2.196(3)
Zn2-O1
2.292(3)
O1-C11
1.209(6)
O2-C24
1.250(5)
O3-C37
1.251(5)
O3-Zn2B
2.196(3)
O4-C50
1.224(5)
N1-C9
1.335(6)
N1-C1
1.391(6)
N2-C10
1.273(5)
N2-N3
1.354(5)
N3-C11
1.373(6)
N4-C14
1.340(6)
N4-C22
1.344(6)
N5-C23
1.258(6)
N5-N6
1.385(5)
N6-C24
1.347(5)
N7-C35
1.304(6)
N7-C27
1.365(5)
N7-Zn2B
2.156(4)
N8-C36
1.261(6)
N8-N9
1.344(5)
N8-Zn2B
2.044(4)
N9-C37
1.363(6)
N10-C48
1.319(6)
N10-C40
1.342(7)
N11-C49
1.261(6)
N11-N12
1.344(6)
N12-C50
1.357(5)
C1-C2
1.381(9)
C1-C6
1.410(7)
C2-C3
1.403(8)
C3-C4
1.397(9)
C4-C5
1.324(10)
C5-C6
1.402(8)
C6-C7
1.390(9)
C7-C8
1.390(7)
C8-C9
1.394(7)
C9-C10
1.411(6)
C11-C12
1.496(6)
C12-C13
1.362(7)
C12-C39
1.398(6)
C13-C25
1.399(6)
C14-C15
1.347(7)
C14-C19
1.453(7)
C15-C16
1.410(8)
C16-C17
1.447(8)
C17-C18
1.331(8)
C18-C19
1.426(8)
C19-C20
1.374(8)
C20-C21
1.346(8)
C21-C22
1.420(7)
C22-C23
1.468(7)
C24-C25
1.523(7)
C25-C26
1.361(6)
C26-C38
1.383(7)
C27-C28
1.384(7)
C27-C32
1.399(7)
C28-C29
1.354(7)
C29-C30
1.408(8)
C30-C31
1.364(8)
C31-C32
1.415(7)
C32-C33
1.385(7)
C33-C34
1.349(7)
C34-C35
1.411(7)
C35-C36
1.491(6)
C38-C39
1.397(6)
C37-C38
1.488(7)
C40-C45
1.435(8)
C40-C41
1.407(7)
C42-C43
1.454(10)
C41-C42
1.395(9)
C44-C45
1.449(10)
C43-C44
1.304(9)
C46-C47
1.369(9)
C45-C46
1.411(8)
C48-C49
1.470(8)
C47-C48
1.401(7)
C51-C52A
1.366(7)
C50-C51
1.506(7)
C52-C51B
1.366(7)
C51-C52
1.417(6)
N5-Zn1-N11
154.0(2)
N5-Zn1-N4
77.0(2)
N11-Zn1-N4
117.9(2)
N5-Zn1-N10
123.7(2)
N11-Zn1-N10
77.1(2)
N4-Zn1-N10
99.6(2)
N5-Zn1-O2
73.3 (1)
N11-Zn1-O2
91.3(1)
N4-Zn1-O2
150.0(1)
N10-Zn1-O2
93.3(1)
N5-Zn1-O4
86.1(2)
N11-Zn1-O4
72.9(1)
N4-Zn1-O4
91.6(2)
N10-Zn1-O4
149.8(1)
O2-Zn1-O4
90.7(1)
N8A-Zn2-N2
150.0(2)
N8A-Zn2-N7A
77.1(1)
N2-Zn2-N7A
121.6(2)
N8A-Zn2-N1
127.5(2)
N2-Zn2-N1
74.8(2)
N7A-Zn2-N1
101.9(2)
N8A-Zn2-O3A
73.2(1)
N2-Zn2-O3A
88.7(2)
N7A-Zn2-O3A
149.3(1)
N1-Zn2-O3A
90.3(1)
N8A-Zn2-O1
83.8(2)
N2-Zn2-O1
72.5(1)
N7A-Zn2-O1
94.0(1)
N1-Zn2-O1
147.3(1)
O3A-Zn2-O1
90.4(1)
Symmetry codes: A. -y+1, x-y, z
B. -x+y+1, -x+1, z
20. Table S3. Selected bond lengths (Å) and angles (°) of compound 3.
Ni1-N2
1.992(4)
Ni1-N2A
1.992(4)
Ni1-O1A
2.090(3)
Ni1-O1
2.090(3)
Ni1-N1
2.093(4)
Ni1-N1A
2.093(4)
O1-C7
1.276(6)
N1-C1
1.342(6)
N1-C5
1.359(6)
C1-C2
1.371(7)
N2-C6
1.300(5)
N2-N3
1.332(5)
C2-C3
1.401(8)
N3-C7
1.330(6)
C3-C4
1.365(7)
C4-C5
1.382(6)
C5-C6
1.444(6)
C7-C8
1.505(7)
C8-C9B
1.353(6)
C8-C9
1.386(6)
C9-C8C
1.353(6)
Ni2-N5
1.969(5)
Ni2-N5D
1.969(5)
Ni2-N4D
2.069(4)
Ni2-N4
2.069(5)
Ni2-O2
2.082(3)
Ni2-O2D
2.082(3)
O2-C17
1.261(6)
N4-C15
1.262(7)
N4-C11
1.347(7)
N5-C16
1.261(6)
N5-N6
1.337(5)
N6-C17
1.310(6)
C11-C12
1.426(8)
C12-C13
1.308(9)
C13-C14
1.362(9)
C14-C15
1.497(8)
C15-C16
1.460(8)
C17-C18
1.495(7)
C18-C19
1.340(6)
C18-C19E
1.441(6)
C19-C18F
1.441(6)
N2-Ni1-N2A
171.0(2)
N2-Ni1-O1A
97.6(1)
N2A-Ni1-O1A
76.0(1)
N2-Ni1-O1
76.0(1)
N2A-Ni1-O1
97.6 (1)
O1A-Ni1-O1
91.9(2)
N2-Ni1-N1
79.4(2)
N2A-Ni1-N1
106.9(2)
O1A-Ni1-N1
91.3(1)
O1-Ni1-N1
155.4(1)
N2-Ni1-N1A
106.9(2)
N2A-Ni1-N1A
79.4(2)
O1A-Ni1-N1A
155.4(1)
O1-Ni1-N1A
91.3(1)
95.9(2)
N1-Ni1-N1A
Symmetry codes: A. -x+5/4,y,-z+1/4
D. -x+3/4,-y+3/4,z
B. z+1/2,-x+7/4,-y+5/4
C. -y+7/4,-z+5/4,x-1/2
E. -z+1/4,-x+3/4,y-1/2 F. -y+3/4,z+1/2,-x+1/4
21. Table S4. Selected bond lengths (Å) and angles (°) of compound 4.
Eu1-O33
2.418(6)
Eu1-O31
2.481(7)
Eu1-O3A
2.487(4)
Eu1-O4
2.488(4)
Eu1-O41
2.535(6)
Eu1-N8A
2.542(6)
Eu1-N11
2.550(5)
Eu1-O42
2.562(6)
Eu1-N7A
2.583(5)
Eu1-N10
2.634(7)
Eu1-N23
2.833(10)
Eu1-N24
2.907(7)
Eu2-O22'
1.863(10)
Eu2-O2
2.441(5)
Eu2-O1
2.473(5)
Eu2-O13
2.484(7)
Eu2-O12
2.487(7)
Eu2-N5
2.520(5)
Eu2-O23
2.531(8)
Eu2-N1
2.555(5)
Eu2-N2
2.575(5)
Eu2-O21
2.600(7)
Eu2-N4
2.641(5)
Eu2-N21
2.808(9)
O1-C7
1.230(8)
O2-C17
1.218(8)
O3-C27
1.269(9)
O3-Eu1B
2.487(4)
O4-C37
1.211(7)
N1-C1
1.312(7)
N1-C5
1.321(6)
N2-C6
1.256(8)
N2-N3
1.345(8)
N3-C7
1.360(8)
N4-C11
1.314(7)
N4-C15
1.334(7)
N5-C16
1.308(8)
N5-N6
1.384(8)
N6-C17
1.355(7)
N7-C25
1.322(7)
N7-C21
1.324(6)
N7-Eu1B
2.583(5)
N8-C26
1.256(9)
N8-N9
1.403(7)
N8-Eu1B
2.542(6)
N9-C27
1.317(9)
N10-C35
1.310(7)
N10-C31
1.313(7)
N11-C36
1.312(11)
N11-N12
1.356(8)
N12-C37
1.361(10)
C1-C2
1.397(7)
C2-C3
1.386(7)
C3-C4
1.399(8)
C4-C5
1.378(7)
C5-C6
1.442(11)
C7-C8
1.497(11)
C8-C9A
1.378(9)
C8-C9
1.401(9)
C9-C8B
1.378(9)
C11-C12
1.372(7)
C12-C13
1.395(7)
C13-C14
1.388(7)
C14-C15
1.388(7)
C15-C16
1.411(10)
C17-C18
1.506(11)
C18-C39
1.372(10)
C18-C19
1.447(8)
C19-C28
1.337(10)
C21-C22
1.381(7)
C22-C23
1.386(8)
C23-C24
1.393(7)
C24-C25
1.382(7)
C25-C26
1.469(9)
C27-C28
1.474(9)
C28-C29
1.384(10)
C29-C38
1.434(9)
C31-C32
1.375(8)
C32-C33
1.379(8)
C33-C34
1.384(8)
C34-C35
1.373(8)
C35-C36
1.348(11)
C37-C38
1.477(10)
C38-C39
1.413(11)
O3A-Eu1-O4
77.8(2)
O3A-Eu1-N8A
62.3(2)
O4-Eu1-N8A
67.9(2)
O3A-Eu1-N11
67.6(2)
O4-Eu1-N11
62.0(2)
N8A-Eu1-N11
114.1(2)
O3A-Eu1-N7A
124.0(2)
O4-Eu1-N7A
74.9(2)
N8A-Eu1-N7A
62.3(2)
N11-Eu1-N7A
132.1(2)
O3A-Eu1-N10
83.5(2)
O4-Eu1-N10
121.7(2)
N8A-Eu1-N10
142.5(2)
N11-Eu1-N10
59.8(2)
N7A-Eu1-N10
151.9(2)
O2-Eu2-O1
81.2(2)
O2-Eu2-N5
62.8 (2)
O1-Eu2-N5
67.7(2)
O2-Eu2-N1
80.2(2)
O1-Eu2-N1
123.3(2)
N5-Eu2-N1
140.0(2)
O2-Eu2-N2
69.3(2)
O1-Eu2-N2
61.7(2)
N5-Eu2-N2
113.5(2)
N1-Eu2-N2
61.6(2)
O2-Eu2-N4
125.5(2)
O1-Eu2-N4
73.9(2)
N5-Eu2-N4
63.0(2)
N1-Eu2-N4
153.0(2)
N2-Eu2-N4
130.7(2)
Symmetry codes: A. -y+1, x-y+1, z B. -x+y, -x+1, z
22. Table S5. Selected bond lengths (Å) and angles (°) of compound 5.
Tb1-O1
2.433(6)
Tb1-O31
2.380(12)
Tb1-O4
2.428(7)
Tb1-O12
2.446(8)
Tb1-O32
2.447(11)
Tb1-O11
2.482(8)
Tb1-N2
2.508(8)
Tb1-N11
2.502(8)
Tb1-N12
2.520(8)
Tb1-N3
2.574(8)
Tb1-N23
2.656(10)
Tb1-N21
2.924(10)
Tb2-O3W
2.49(2)
Tb2-O42
2.426(10)
Tb2-O3A
2.403(6)
Tb2-O2
2.415(6)
Tb2-O22
2.403(11)
Tb2-O43
2.419(11)
Tb2-N8A
2.453(9)
Tb2-N5
2.510(8)
Tb2-N6
2.552(10)
Tb2-N9A
2.515(9)
Tb2-O23
2.560(10)
Tb2-N24
2.749(12))
C1-C2
1.366(12)
C1-C6
1.421(11)
C1-C7
1.569(14)
O1-C7
1.315(12)
O2-C14
1.296(11)
O3-C21
1.198(12)
N1-C7
1.287(12)
O4-C30
1.214(11)
N2-C8
1.211(11)
N1-N2
1.336(10)
N3-C13
1.274(12)
N3-C9
1.320(13)
N4-N5
1.457(10)
N4-C14
1.337(12)
N6-C20
1.309(13)
N5-C15
1.278(12)
N7-C21
1.380(12)
N6-C16
1.328(13)
N8-C22
1.276(12)
N7-N8
1.370(10)
N9-C23
1.258(14)
N9-C27
1.289(13)
N10-N11
1.360(11)
N10-C30
1.335(11)
N12-C36
1.189(15)
N11-C31
1.335(12)
C2-C3
1.399(13)
N12-C32
1.281(13)
C3-C14
1.490(13)
C3-C4
1.328(12)
C5-C6
1.405(13)
C4-C5
1.329(12)
C8-C9
1.537(15)
C5-C21
1.538(13)
C10-C11
1.397(17)
C9-C10
1.345(14)
C12-C13
1.297(14)
C11-C12
1.316(16)
C16-C17
1.337(15)
C15-C16
1.405(13)
C18-C19
1.468(17)
C17-C18
1.360(16)
C22-C23
1.474(15)
C19-C20
1.367(16)
C24-C25
1.429(16)
C23-C24
1.433(16)
C26-C27
1.314(16)
C25-C26
1.363(18)
C28-C29A
1.465(13))
C28-C29
1.385(11))
C32-C33
1.440(14)
C29-C30
1.427(14)
C34-C35
1.319(19)
C31-C32
1.520(15)
C33-C34
1.413(19)
C35-C36
1.426(18)
O1-Tb1-O4
81.2(2)
O1-Tb1-N2
62.2(2)
O31-Tb1-N2
117.1(3)
O4-Tb1-N2
68.6(3)
O1-Tb1-N11
70.9(2)
O4-Tb1-N11
62.0(2)
N2-Tb1-N11
115.1(3)
O1-Tb1-N12
79.5(3)
O4-Tb1-N12
126.7(2)
N2-Tb1-N12
136.9(3)
N11-Tb1-N12
64.8(3)
O1-Tb1-N3
126.9(3)
O4-Tb1-N3
82.0(3)
N2-Tb1-N3
64.7(3)
N11-Tb1-N3
137.9(3)
N12-Tb1-N3
146.4(3)
O3A-Tb2-N8A
62.8(2)
O2-Tb2-N8A
69.3(3)
O3A-Tb2-N5
68.0(3)
O2-Tb2-N5
63.5(3)
N8A-Tb2-N5
115.2(3)
O3A-Tb2-N6
80.8(3)
O2-Tb2-N6
125.0(3)
N8A-Tb2-N6
139.1(3)
N5-Tb2-N6
61.5(3)
O3A-Tb2-N9A
126.9(3)
O2-Tb2-N9A
78.0(3)
N8A-Tb2-N9A
64.2(3)
N5-Tb2-N9A
136.5(3)
Symmetry code A. -x+y-1, -x, z
N6-Tb2-N9A
149.0(3)