Intra-Cation versus Inter-Cation π-Contacts in [Cu(P^P)(N^N)][PF6] Complexes
Abstract
:1. Introduction
2. Materials and Methods
2.1. General
2.2. [Cu(POP)(1)][PF6]
2.3. [Cu(xantphos)(1)][PF6]
2.4. [Cu(POP)(2)][PF6]
2.5. [Cu(xantphos)(2)][PF6]
2.6. [Cu(POP)(3)][PF6]
2.7. [Cu(xantphos)(3)][PF6]
2.8. Crystallography
2.9. [Cu(xantphos)(1)][PF6]·CH2Cl2
2.10. [Cu(xantphos)(2)][PF6]·CH2Cl2
2.11. [Cu(POP)(3)][PF6]·0.5H2O
3. Results and Discussion
3.1. Synthesis and Mass Spectrometric and NMR Spectroscopic Characterization of the Copper(I) Compounds
3.2. Crystal Structures of [Cu(xantphos)(1)][PF6]·CH2Cl2, [Cu(xantphos)(2)][PF6]·CH2Cl2 and [Cu(POP)(3)][PF6]·0.5H2O
3.3. Electrochemical and Photophysical Properties
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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[Cu(P^P)(N^N)]+ Cation | Cu–N/Å | Cu–P/Å | P–Cu–P/o | N–Cu–N/o | τ4 1 |
---|---|---|---|---|---|
[Cu(xantphos)(1)]+ | 2.1142(13), 2.0796(13) | 2.2589(5), 2.3038(5) | 116.050(17) | 79.05(5) | 0.83 |
[Cu(xantphos)(2)]+ | 2.0654(18), 2.0693(18) | 2.2241(6), 2.2729(6) | 120.05(2) | 79.45(7) | 0.82 |
[Cu(POP)(3)]+ | 2.060(2), 2.127(2) | 2.2789(7), 2.2662(7) | 112.83(3) | 79.68(8) | 0.89 |
Cation in [Cu(P^P)(N^N)][PF6] | E1/2ox/V | Epc − Epa/mV | E1/2red/V | Epc − Epa/mV |
---|---|---|---|---|
[Cu(POP)(1)]+ | +0.92 a | - | −2.21, −2.11 b | - |
[Cu(xantphos)(1)]+ | +0.87 | 80 | −2.18, −2.10 b | - |
[Cu(POP)(2)]+ | +0.81 | 100 | −2.04 | 130 |
[Cu(xantphos)(2)]+ | +0.84 | 110 | −2.00 | 130 |
Cation in [Cu(P^P)(N^N)][PF6] | λmax/nm (ε/dm3 mol−1 cm−1) | |
---|---|---|
Ligand-Based Absorptions | MLCT | |
[Cu(POP)(1)]+ | 260 sh (40,000), 272 (42,600), 308 sh (24,100), 322 sh (16,300) | 390 (4100) |
[Cu(xantphos)(1)]+ | 253 sh (38,500), 274 (45,200), 321 sh (15,100) | 390 (4100) |
[Cu(POP)(2)]+ | 276 (35,500), 333 (30,200) | 400 (2700) |
[Cu(xantphos)(2)]+ | 277 (41,450), 333 (26,200) | 400 (2700) |
Cation in [Cu(P^P)(N^N)][PF6] | λexc/nm | λem/nm | PLQY a (Non-Deaerated)/% | PLQY a (Deaerated)/% |
---|---|---|---|---|
[Cu(POP)(1)]+ | 365 | 575 | 2 | 20 |
[Cu(xantphos)(1)]+ | 365 | 570 | 1 | 12 |
[Cu(POP)(2)]+ | 365 | 500 | 3 | 10 |
[Cu(xantphos)(2)]+ | 365 | 500 | 3 | 10 |
Cation in [Cu(P^P)(N^N)][PF6] | λexc/nm | λem/nm | PLQY/% | τ1/2/μs |
---|---|---|---|---|
[Cu(POP)(1)]+ | 365 | 535 | 41 | 9.4 |
[Cu(xantphos)(1)]+ | 365 | 560 | 35 | 11.1 |
[Cu(POP)(2)]+ | 365 | 560 | 27 | 9.2 |
[Cu(xantphos)(2)]+ | 365 | 577 | 19 | 5.0 |
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Mazzeo, F.; Brunner, F.; Prescimone, A.; Constable, E.C.; Housecroft, C.E. Intra-Cation versus Inter-Cation π-Contacts in [Cu(P^P)(N^N)][PF6] Complexes. Crystals 2020, 10, 1. https://doi.org/10.3390/cryst10010001
Mazzeo F, Brunner F, Prescimone A, Constable EC, Housecroft CE. Intra-Cation versus Inter-Cation π-Contacts in [Cu(P^P)(N^N)][PF6] Complexes. Crystals. 2020; 10(1):1. https://doi.org/10.3390/cryst10010001
Chicago/Turabian StyleMazzeo, Francesca, Fabian Brunner, Alessandro Prescimone, Edwin C. Constable, and Catherine E. Housecroft. 2020. "Intra-Cation versus Inter-Cation π-Contacts in [Cu(P^P)(N^N)][PF6] Complexes" Crystals 10, no. 1: 1. https://doi.org/10.3390/cryst10010001