Synthesis, Spectroscopic Characterization, and Photophysical Studies of Heteroleptic Silver Complexes Bearing 2,9-Bis(styryl)-1,10-phenanthroline Ligands and Bis[(2-diphenylphosphino)phenyl] Ether
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterization
2.2. Characterization in Solution
2.3. Optical-Photophysical Properties of Ligands in Solution
2.4. Optical Properties of Complexes in Solution
2.5. Luminescent Behavior in Solid State
2.6. Single-Crystal Structure Analysis
2.7. Computational Study
3. Materials and Methods
3.1. Materials
3.2. Methods
3.3. Crystal Structure Determination
3.4. Computational Details
3.5. Synthesis of Complexes
- [Ag(L1)(POP)][BF4] (1)
- [Ag(L2)(POP)][BF4] (2)
- [Ag(L3)(POP)][BF4] (3)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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H Atoms | 1 | 2 | 3 | Δδ (1) * | Δδ (2) * | Δδ (3) * |
---|---|---|---|---|---|---|
H(3)/H(8) | 8.24 | 8.28 | 8.14 | 0.31 | 0.34 | 0.24 |
H(4)/H(7) | 8.44 | 8.48 | 8.32 | 0.22 | 0.25 | 0.16 |
H(5)/H(6) | 7.83 | 7.86 | 7.77 | 0.09 | 0.11 | 0.09 |
H(a) | 7.48 | 7.51 | 7.39 | −0.29 | −0.26 | −0.33 |
H(b) | 7.42 | 7.48 | 7.30 | −0.2 | −0.21 | −0.24 |
A, H(2,6) | 6.85 | 6.95 | 6.70 | −0.83 | −0.69 | −0.9 |
A, H(3,5) | 6.65 | 6.81 | 6.33 | −0.34 | −0.51 | −0.4 |
(-OMe) (-CH3) | 3.88 | - | - | −0.02 | - | - |
(-SMe) (-CH3) | - | 2.56 | - | - | 0 | - |
(-NEt2) (-CH2) | - | - | 3.42 | - | - | −0.03 |
(-NEt2) (-CH3) | - | - | 1.25 | - | - | −0.01 |
POP(C ring) H3 | 6.73 | 6.74 | 6.85 | 0.01 | 0.02 | 0.13 |
POP(C ring) H4 | 7.19 | 7.21 | 7.02 | −0.03 | −0.01 | −0.20 |
POP(C ring) H5 | 7.12 | 7.12 | 7.15 | 0.13 | 0.13 | 0.16 |
POP(C ring) H6 | 6.91 | 6.92 | 6.93 | 0.07 | 0.08 | 0.09 |
Compound | λabs/nm (ε/Μ−1cm−1) (CH2Cl2) | λem/nm (CH2Cl2) | Φem (CH2Cl2) | λem/nm (Solid) | Φem (Solid) |
---|---|---|---|---|---|
L2 | 235 (44,000), 332 (60,000), 377 (48,000) | 460 | 10% | - | - |
L3 | 239 (45,454), 360 (40,184), 407 (62,582) | 538 | 6% | - | - |
Compound | λabs/nm (ε/Μ−1cm−1) (CH2Cl2) | λem/nm (CH2Cl2) | Φem (CH2Cl2) | λem/nm (Solid) | Φem (Solid) |
---|---|---|---|---|---|
1 | 230 (96,153), 335 (62,500), 385 (65,384) | 445 | 11% | 487 | 9.5% |
2 | 235 (63,532), 350 (55,908), 390 (60,991) | 465 | 20% | 534 | 5.6% |
3 | 245 (56,112), 445 (80,160) | 550 | 23% | 625 | 2.5% |
Bond Distances | (Å) | Bond Angles | (°) |
---|---|---|---|
Ag(1)-N(1) | 2.350(3) | N(1)-Ag(1)-N(2) | 72.11(12) |
Ag(1)-N(2) | 2.356(4) | N(1)-Ag(1)-P(2) | 127.15(9) |
Ag(1)-P(2) | 2.4104(12) | N(2)-Ag(1)-P(2) | 133.36(9) |
Ag(1)-P(1) | 2.5661(12) | N(1)-Ag(1)-P(1) | 97.05(9) |
N(2)-Ag(1)-P(1) | 96.20(9) | ||
P(2)-Ag(1)-P(1) | 118.64(4) |
Bond Distances | (Å) | Bond Angles | (°) |
---|---|---|---|
Ag(1)-N(1) | 2.385(3) | N(1)-Ag(1)-N(2) | 70.43(11) |
Ag(1)-N(2) | 2.392(3) | N(1)-Ag(1)-P(2) | 114.60(9) |
Ag(1)-P(2) | 2.5240(12) | N(2)-Ag(1)-P(2) | 118.77(8) |
Ag(1)-P(1) | 2.5245(12) | N(1)-Ag(1)-P(1) | 117.89(8) |
N(2)-Ag(1)-P(1) | 110.36(9) | ||
P(2)-Ag(1)-P(1) | 116.67(4) |
Bond Distances | (Å) | Bond Angles | (°) |
---|---|---|---|
Ag(1)-N(1) | 2.362(4) | N(1)-Ag(1)-N(2) | 71.13(12) |
Ag(1)-N(2) | 2.377(4) | N(1)-Ag(1)-P(2) | 114.57(9) |
Ag(1)-P(2) | 2.5117(14) | N(2)-Ag(1)-P(2) | 118.83(9) |
Ag(1)-P(1) | 2.5144(13) | N(1)-Ag(1)-P(1) | 116.75(9) |
N(2)-Ag(1)-P(1) | 113.40(9) | ||
P(2)-Ag(1)-P(1) | 115.11(5) |
Excitation (% Composition) | λ (nm) | f | Assignment |
---|---|---|---|
1 | |||
H → L (90%) | 397 | 0.723 | MLCT/IL/LL’CT |
H-1 → L (62%), H → L + 1 (27%), H-2 → L + 1 (8%) | 356 | 0.352 | IL/LL’CT |
H → L + 2 (77%), H-2 → L + 1 (5%), H-2 → L + 2 (5%) | 324 | 0.482 | MLCT/IL/LL’CT |
H → L + 4 (38%), H-2 → L + 3 (23%), H → L + 3 (11%), H-2 → L + 4 (10%) | 285 | 0.056 | IL/LL’CT |
H-12 → L (16%), H-5 → L + 1 (16%), H-9 → L + 1 (13%) | 263 | 0.058 | IL/LL’CT |
H-2 → L + 6 (35%), H → L + 6 (17%), H → L + 9 (10%) | 255 | 0.087 | IL/LL’CT |
2 | |||
H → L (94%) | 420 | 0.846 | IL |
H-1 → L (90%), H → L + 1 (6%) | 400 | 0.575 | IL |
H-1 → L + 1 (92%) | 358 | 0.136 | IL |
H-6 → L (55%), H-4 → L + 1 (16%) | 299 | 0.093 | IL |
H-6 → L + 1 (38%), H-8 → L (9%), H-3 → L + 2 (9%) | 278 | 0.078 | IL |
H-4 → L + 2 (34%), H-12 → L (17%) | 266 | 0.089 | IL |
3 | |||
H → L (90%), H-1 → L (6%) | 475 | 0.827 | IL |
H-1 → L (90%), H → L (7%) | 431 | 0.658 | IL |
H → L + 2 (95%) | 372 | 0.540 | IL |
H-4 → L (83%) | 306 | 0.078 | IL |
H → L + 9 (48%), H → L + 11 (12%) | 285 | 0.160 | IL |
H-11 → L (28%), H-2 → L + 6 (26%), H-1 → L + 11 (19%) | 264 | 0.098 | IL |
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Glykos, D.; Tsipis, A.C.; Plakatouras, J.C.; Malandrinos, G. Synthesis, Spectroscopic Characterization, and Photophysical Studies of Heteroleptic Silver Complexes Bearing 2,9-Bis(styryl)-1,10-phenanthroline Ligands and Bis[(2-diphenylphosphino)phenyl] Ether. Inorganics 2024, 12, 131. https://doi.org/10.3390/inorganics12050131
Glykos D, Tsipis AC, Plakatouras JC, Malandrinos G. Synthesis, Spectroscopic Characterization, and Photophysical Studies of Heteroleptic Silver Complexes Bearing 2,9-Bis(styryl)-1,10-phenanthroline Ligands and Bis[(2-diphenylphosphino)phenyl] Ether. Inorganics. 2024; 12(5):131. https://doi.org/10.3390/inorganics12050131
Chicago/Turabian StyleGlykos, Dimitrios, Athanassios C. Tsipis, John C. Plakatouras, and Gerasimos Malandrinos. 2024. "Synthesis, Spectroscopic Characterization, and Photophysical Studies of Heteroleptic Silver Complexes Bearing 2,9-Bis(styryl)-1,10-phenanthroline Ligands and Bis[(2-diphenylphosphino)phenyl] Ether" Inorganics 12, no. 5: 131. https://doi.org/10.3390/inorganics12050131