Materials And Methods
All chemical solvents and reagents used in analytical tests were purchased commercially and used without further purification. Elemental analyses (C, H, and O) were carried out on the Elementar Vario ELIII analyzer. The Fourier-transform Infrared (FT-IR) spectra were collected by NICOLET-IS10 spectrometer in the range of 400–4000 cm− 1 with KBr pellets. Powder X-ray diffraction (PXRD) patterns were attained by a Bruker D8 ADVANCE A25X diffractometer with a scan speed of 12 °/min. Thermogravimetric analyses (TGA) were obtained on a STA449F31 thermogravimetric analyzer from ambient temperature to 800°C under a N2 atmosphere. Fluorescence spectra were performed on GARY ECLIPS spectrometer at room temperature.
Synthesis Of 1,1'-((2,3,5,6-tetramethyl-1,4-phenylene)bis(Methylene))bis(4-carboxypyridin-1-ium)chloride (Hlcl)
The ligand 1,1'-((2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene))bis(4-carboxypyridin-1-ium)chloride (H2LCl2) was synthesized by the method of the Scheme 1. Firstly, ethyl isonicotinate (7.500 g, 49.5 mmol) and 1,4-bis(chloromethyl)-2,3,5,6-tetramethylbenzene (5.2100 g, 22.5 mmol) were dissolved in 150 mL acetonitrile for reflux reaction for two days. When the complex was cooled to room temperature, the product was filtered out and washed three times with acetonitrile to obtain a white powder after drying. Then dissolve the white dry powder in 100 mL HCl/H2O (v:v = 2:1) mixture solvent, and reflux and stir for 12 h to obtain a white solid. Ligand H2LCl2 was attained when washed with water (yield:90%). IR (KBr, cm− 1): 3429.44, 3122.18, 2139.12, 1778.55, 1685.72, 1634.41, 1447.25, 1388.22, 1241.88, 1114.87, 906.71, 760.97, 674.45, 514.00
Synthesis Of Hlclo·ho
The H2LCl2 (0.0096g, 0.02 mmol) and NaOH (0.0016g, 0.04 mmol) were weighed and dissolved in 2 mL H2O, then NaClO4 (0.0049 g, 0.04 mmol), 1 mL ethanol and 1 mL DMF were added and stirred for 30 min at room temperature to obtain a white flocculent solution. The resulting reaction solution was filtered, and the filtrate was allowed to evaporate at room temperature. After two weeks, colorless transparent crystal particles with a yield of 35.7% (based on H2LCl2) were obtained for X-single crystal diffraction testing.
Synthesis Of [cd(L)(So)(Ho)][cd(Ho)]·4ho (Cp 1)
The synthesis method and dosage of CP 1 are similar to that of the HLClO4·H2O; just change the metal salt from NaClO4 to CdSO4‧8/3H2O (0.0103g, 0.04 mmol). Finally, after three weeks of reaction at room temperature, a colorless block crystal of complex CP 1 was obtained, with a yield of 25.6% (based on H2LCl2). Elemental Analysis (%): cacld for C48H72Cd2N4O28S2 (Mr = 1442.05): C, 39.98%; H, 5.03%; O, 31.06%. Found: C, 39.77%; H, 5.06%; O, 31.34%. IR (KBr, cm− 1): 3418.39, 3110.32, 1613.70, 1563.93, 1449.63, 1383.40, 1125.45, 775.28, 618.71.
X-ray Crystallography Diffraction
Single crystal X-ray diffraction data of HLClO4·H2O were performed on a Bruker APEX-II CCD. The Crystallographic data of CP 1 were obtained on XtaLAB Pro: Kappa single equipment. The structures were solved by direct methods and refined using the SHELXTL program package and Olex2 [22]. The solvent water molecules in CP 1 were distorted, and the SQUEEZE method in the PLATON program was applied to subtract the guest molecules. The final formula of CP1 was speculated by combining the crystal structure, TGA, and elemental analysis. The details of structure refinements and crystallographic data of HLClO4·H2O and CP 1 are displayed in Table 1. And a portion of bond lengths and angles are calculated in Table 2 and Table 3.
Table 1
Crystal data and structure refinement of HLClO4·H2O and CP 1
Compound | HLClO4·H2O | CP 1 |
Formula | C24H27ClN2O9 | C48H72Cd2N4O28S2 |
Formula weight | 522.92 | 1442.05 |
Crystal system | Monoclinic | Triclinic |
Space group | P21/n | P-1 |
a/Å | 9.5964(9) | 10.9341(3) |
b/Å | 21.316(2) | 11.6484(3) |
c/Å | 12.5830(12) | 14.0370(4) |
α/° | 90 | 107.831(2) |
β/° | 109.8400(10) | 108.144(2) |
γ/° | 90 | 92.333(2) |
V/Å 3 | 2421.1(4) | 1598.92(8) |
Z | 4 | 1 |
Dc /(g·cm− 3 ) | 1.435 | 1.423 |
µ/mm–1 | 0.215 | 0.805 |
F(000) | 1096.0 | 700.0 |
Reflection collected | 22661 | 29849 |
Independent reflections | 5622 | 8572 |
Rint | 0.0420 | 0.0288 |
GOF on F2 | 1.060 | 1.128 |
R1, wR2[I > 2σ(I)] | 0.0651, 0.1899 | 0.0348, 0.1119 |
R1, wR2 (all date) | 0.1161, 0.2230 | 0.0404, 0.1150 |
R1 = ∑|Fo|−|Fc|/ ∑|Fo|; wR2 = [∑w(Fo2−Fc2)2/∑w(Fo2)2]1/2 |
Table 2
Selected bond lengths (Å) and bond angles (°) of HLClO4·H2O and CP 1
HLClO4·H2O |
C1 − C2 | 1.514(5) | C7 − C8 | 1.512(4) |
C1 − O1 | 1.295(5) | C7 − N1 | 1.511(3) |
C2 − C3 | 1.382(4) | C8 − C9 | |
C4 − N1 | 1.358(4) | C13 − C16 | |
O2 − C1 − O1 | 126.1(3) | N1 − C7 − C8 | 112.8(2) |
C3 − C2 − C1 | 119.2(3) | C4 − C3 − C2 | 119.6(3) |
C5 − N1 − C4 | 121.3(3) | C13 − C12 − C11 | |
CP 1 |
Cd1 − O1 | 2.2727(16) | Cd2 − O10 | 2.2762(19) |
Cd1 − O5 | 2.2946(17) | Cd2 − O11 | 2.301(2) |
Cd1 − O6 | 2.3178(18) | Cd2 − O12 | 2.275(2) |
Cd1 − O1#1 | 2.2726(16) | Cd2 − O10#2 | 2.276(2) |
C4 − N1 | 1.350(3) | O7 − S1 | 1.475(2) |
O1 − Cd1 − O5 | 90.93(7) | C4 − N1 − C6 | 120.88(19) |
O1#1−Cd1 − O6 | 88.30(7) | O10 − Cd2 − O11 | 91.02(8) |
O6 − Cd1 − O6#1 | 180.00(6) | O10#2−Cd2 − O11 | 88.98(8) |
C19 − C20 − C21 | 119.5(2) | O3 − C24 − O4 | 127.1(2) |
C4 − N1 − C7 | 117.39(18) | O7 − S1 − O6 | |
Symmetry transformations used to generate equivalent atoms: CP1, #1 -x, 1-y, 1-z; #2 1-x, -y, 1-z.
Table 3
The hydrogen bond lengths [Å] and bond angles [°] for HLClO4·H2O and CP 1
HLClO4·H2O |
D − H···A d(D − H)/Å d(H···A)/Å d(D − A)/Å ∠DHA/(°) |
O1 − H1···O3#1 | 0.86(4) | 1.67(4) | 2.514(3) | 170(4) |
O1 − H1···O4#1 | 0.86(4) | 2.58(4) | 3.020(4) | 113(3) |
O9 − H9A···O4#2 | 0.85 | 1.88 | 2.704(4) | 163 |
O9 − H9B···O7#2 | 0.85 | 2.21 | 2.962(5) | 148 |
C3 − H3···O7#3 | 0.93 | 2.51 | 3.107(5) | 122 |
C4 − H4···O7#3 | 0.93 | 2.51 | 3.108(5) | 123 |
C4 − H4···O9#4 | 0.93 | 2.43 | 3.331(5) | 163 |
C7 − H7A···O2#5 | 0.97 | 2.59 | 3.379(5) | 138 |
C15 − H15C···N2 | 0.96 | 2.62 | 3.233(6) | 122 |
CP 1 |
D − H···A d(D − H)/Å d(H···A)/Å d(D − A)/Å ∠DHA/(°) |
O10 − H10A···O4#5 | 0.85 | 1.86 | 2.683(3) | 161 |
O11 − H11b···O2#4 | 0.85 | 2.51 | 2.893(3) | 108 |
O12 − H12B···O7#2 | 0.85 | 2.05 | 2.705(4) | 134 |
C23 − H23···O6#3 | 0.93 | 2.47 | 3.367(3) | 162 |
O5 − H5A···O2#1 | 0.89 | 1.95 | 2.731(3) | 146 |
O5 − H5B···O9#1 | 0.89 | 1.92 | 2.716(3) | 148 |
Symmetry transformations used to generate equivalent atoms: HLClO4·H2O, #1 1/2-x, -1/2 + y, 5/2-z; #2 − 1/2 + x, 1/2-y, -1/2 + z; #3 1/2-x, -1/2 + y, 3/2-z; #4 -x, -y, 1-z; #5 − 1/2 + x, -1/2-y, -1/2 + z; CP 1, #1 -x, 1-y, 1-z; #2 1-x, -y, 1-z; #3-1-x, 1-y, -z ; #4 1 + x, y, z; #5-x, 1-y, -z.