Inorganic Chemistry
Article
= 2:1) and recrystallized from chloroform/ethanol to obtain L1 as
yellow solid. Yield: 68% (0.29 g). Mp: 120.0−130.0 °C. H NMR
(400 MHz, CD2Cl2): δ 8.48 (s, 2H), 8.02 (d, J = 8.3 Hz, 4H), 7.58−
7.62 (m, 8H), 7.48 (d, 4H, J = 7.1), 7.40 (t, 4H, J = 7.4), 7.22−7.32
(m, 12H), 7.14 (m, 2H), 3.61 (s, 4H), 3.57 (s, 4H), 2.84 (s, 16H).
13C NMR (100 MHz, CDCl3): 140.60, 140.01, 137.58, 137.15,
131.77, 131.24, 130.59, 129.49, 129.40, 128.58, 128.44, 127.18,
126.92, 126.64, 125.61, 125.44, 60.53. 60.40. Anal. Calcd for
[C64H60N4 + 1.5H2O]: C, 84.27; H, 6.96; N, 6.14. Found: C,
83.99; H, 6.67; N, 6.23%. FAB-MS (m/z) (DTT:TG = 1:1): 886 ([M
+ 1]+, 40%).
equiv of metal salts to the L1 and L2 THF solutions, the fluorescence
spectroscopies were measured. The excitation wavelengths (λex) for
L1 and L2 were 365 and 342.5 nm, respectively.
Metal-Induced Fluorescence Change in the Solid State. To
preparation for solid-state metal complexes of L1, metal nitrate salts
(0.020 mmol) in methanol (1 mL) were added to a solution of L1
(17.7 mg, 0.020 mmol) in chloroform. Acetonitrile and 1,2-
dichloroethane were added to the mixture to dissolve a fine powder
that precipitated the solution. The mixture was slowly evaporated
until a solid product was afforded. Obtained solid products were
confirmed by elemental analysis.
1
[Ag(NO3)L1]: Anal. Calcd for [C64H60N5O3Ag + 2CHCl3]: C,
61.27; H, 4.83; N, 5.41. Found: C, 61.28; H, 4.99; N, 5.59%.
[Cu(NO3)2L1]: Anal. Calcd for [C64H60N6O6Cu + 0.5CHCl3]: C,
68.41; H, 5.38; N, 7.42. Found: C, 68.47; H, 5.62; N, 7.61%.
[Zn(NO3)2L1]: Anal. Calcd for [C64H60N6O6Zn + 0.25CHCl3]: C,
69.87; H, 5.50; N, 7.61. Found: C, 69.90; H, 5.63; N, 7.54%.
[Cd(NO3)2L1]: Anal. Calcd for [C64H60N6O6Cd + 2.4CHCl3 +
6CH3CN]: C, 56.92; H, 4.90; N, 10.16. Found: C, 57.10; H, 5.11; N,
10.34%.
Synthesis of 1,7-Bis(4-(1-pyrenyl)benzyl)-4,10-dibenzyl-
1,4,7,10-tetraazacyclododecane (L2). 1,7-Dibenzylcyclen38 (1,
0.178 g, 0.5 mmol), 4-(1-pyrenyl)benzaldehyde (3, 0.616 g, 2.0
mmol), and NaBH(OAc)3 (0.44 g, 2.1 mmol) were added to 1,2-
dichloroethane (10 mL) under a nitrogen atmosphere. The mixture
was stirred for 7 days at room temperature. Saturated aqueous
Na2CO3 was then added before the mixture was extracted with
chloroform. The combined organic phases were dried with anhydrous
sodium sulfate and then evaporated to dryness. The residue was
separated by silica gel column chromatography (chloroform:metha-
nol:ammonia = 5:1:0.2) and recrystallized from chloroform/
acetonitrile to obtain L2 as yellow solid. Yield: 78% (0.37 g). Mp:
[Hg(NO3)2L1]: Anal. Calcd for [C64H60N6O6Hg + 0.5CHCl3]: C,
61.02; H, 4.80; N, 6.62. Found: C, 61.15; H, 4.82; N, 6.80%.
The metal nitrate salts (0.020 mmol) in methanol (1 mL) were
added to a solution of L2 (18.6 mg, 0.020 mmol) in chloroform.
Acetonitrile was added to the mixture for dissolving a fine powder that
precipitated from the solution. The mixture was slowly evaporated
until a solid product was afforded. Obtained solid products were
confirmed by elemental analysis.
1
182.0−184.0 °C (dec.). H NMR (400 MHz, CD2Cl2): δ 8.20−7.18
(m, 36H), 3.60 (s, 4H), 3.56 (s, 4H), 2.84 (s, 16H). 13C NMR (100
MHz, CD2Cl2): 139.65, 138.25, 131.88, 131.35, 130.79, 130.64,
129.43, 129.37, 128.78, 128.45, 128.09, 127.78, 127.67, 127.62,
126.93, 126.37, 125.68, 125.38, 125.26, 125.19, 125.10, 125.01, 60.57,
60.30. Anal. Calcd for [C68H60N4 + 1.5H2O]: C, 85.05; H, 6.61; N,
5.83. Found: C, 85.25; H, 6.40; N, 5.88%. FAB-MS (m/z) (DTT:TG
= 1:1): 933 ([M + 1]+, 10%).
[Ag(NO3)L2]: Anal. Calcd for [C68H60N5O3Ag + H2O]: C, 72.85;
H, 5.57; N, 6.25. Found: C, 72.76; H, 5.46; N, 6.06%.
[Ni(NO3)2L2]: Anal. Calcd for [C68H60N6O6Ni + 0.5CHCl3
+
Preparation of [Ag(BF4)L1], [Ag(L1)]·BF4·3CHCl3. AgBF4 (3.9
mg, 0.020 mmol) in methanol (1 mL) was added to a solution of L1
(17.7 mg, 0.020 mmol) in chloroform (1 mL). Acetonitrile and 1,2-
dichloroethane were added to the mixture to dissolve a fine powder
that precipitated the solution. The slow evaporation of the solution
afforded a colorless crystalline product ([Ag(BF4)L1]) suitable for X-
ray analysis. Because the sample was dried under vacuum for the
elemental analysis sample, some lattice solvent (CHCl3) was reduced.
Mp: 125.0−130.0 °C (dec.). Anal. Calcd for [C64H60N4B1F4Ag1 +
1.5CHCl3 + 0.5H2O]: C, 62.05; H, 4.97; N, 4.42. Found: C, 61.91; H,
4.93; N, 4.24%.
0.5H2O]: C, 69.45; H, 5.23; N, 7.09. Found: C, 69.25; H, 5.52; N,
7.29%.
[Cu(NO3)2L2]: Anal. Calcd for [C68H60N6O6Cu + 0.5CHCl3 +
H2O]: C, 68.65; H, 5.35; N, 7.01. Found: C, 68.72; H, 5.35; N,
7.28%.
[Zn(NO3)2L2]: Anal. Calcd for [C68H60N6O6Zn + 1.5H2O]: C,
71.04; H, 5.52; N, 7.31. Found: C, 70.99; H, 5.34; N, 7.28%.
[Hg(NO3)2L2]: Anal. Calcd for [C68H60N6O6Hg + 0.5CHCl3]: C,
62.45; H, 4.63; N, 6.38. Found: C, 62.66; H, 4.74; N, 6.58%.
X-ray Crystallographic Analysis. X-ray data were collected on a
Bruker SMART APEX II ULTRA diffractometer equipped with
graphite monochromated Mo Kα radiation (λ = 0.71073 Å)
generated by a rotating anode. The cell parameters for the compounds
were obtained from a least-squares refinement of the spot. Data
collection, data reduction, and semiempirical absorption correction
were carried out using the software package of APEX2.58 All of the
calculations for the structure determination were carried out using the
SHELXTL package.59 In all cases, non-hydrogen atoms were refined
anisotropically and hydrogen atoms were placed in idealized positions
and refined isotropically in a riding manner along with their respective
parent atoms. Relevant crystal data collection and refinement data for
the crystal structures are summarized in Table S1. Crystallographic
CCDC.
Preparation of [Ag(OTf)L2], [Ag(L2)]·OTf·2CHCl3. AgOTf (5.1
mg, 0.020 mmol) in methanol (1 mL) was added to a solution of L2
(18.6 mg, 0.020 mmol) in chloroform (1 mL). The acetonitrile was
added to the mixture for dissolving a fine powder that precipitated
from the solution. The slow evaporation of the solution afforded a
colorless crystalline product ([Ag(OTf)L2]) suitable for X-ray
analysis. Because the sample was dried under vacuum for the
elemental analysis sample, lattice solvent (CHCl3) was removed. Anal.
Calcd for [C69H60N4O3F3S1Ag + H2O]: C, 68.59; H, 5.17; N, 4.64.
Found: C, 68.79; H, 5.08; N, 4.52%.
UV−Vis Titration with AgOTf for L1 and L2. All titrations were
performed in a mixed solvent of chloroform and methanol (1:9). For
titration, 1.25 × 10−5 and 1.25 × 10−5 M solutions of L1 and L2 were
prepared, respectively. Both titrations were performed with the 0.0−
6.0 equiv of silver(I) triflate. Titration data were fitted into a desired
binding model with HyperSpec.57
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
Fluorescence Titration with AgOTf for L1 and L2. All titrations
sı
were performed in a THF solvent. The 2.0 × 10−7 and 2.0 × 10−5
M
solutions of L1 and L2 were prepared, respectively. The titration of L1
was performed with 0.0−3.0 equiv of silver(I) triflate. In the case of
L2, titration was performed with the 0.0−10.0 equiv of silver(I)
triflate. Also, titration data were fitted into a desired binding model
with HyperSpec.57 The excitation wavelengths (λex) for L1 and L2
were 365 and 342.5 nm, respectively.
NMR spectra, UV−vis spectra PL spectra, crystal
structures, and CSI-MS spectra (PDF)
Accession Codes
tallographic data for this paper. These data can be obtained
Metal-Induced Fluorescence Change in a Solution. Metal
ion-induced fluorescence spectral changes were carried out. THF
solutions of metal salts (AgNO3, Ni(NO3)2, Cu(NO3)2, Zn(NO3)2,
Cd(NO3)2, and Hg(NO3)2) were prepared. After the addition of 1.0
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Inorg. Chem. 2021, 60, 9141−9147