联三吡啶铂(Ⅱ)配合物的非线性吸收和光限幅（特邀）
Nonlinear absorption and optical limiting of platinum(Ⅱ) terpyridine complexes (Invited)
北达克达州立大学 化学与生物化学系，美国 北达克达州法戈市 58108-6050
图 & 表
图 1.
Fig. 1. Representative structures for the most commonly studied square-planar Pt(II) complexes
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图 2.
Fig. 2. Structures of Pt(Ⅱ) terpyridine acetylide complexes 1-22 with different substituents on the acetylide ligand or on the terpyridine ligand
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图 3.
Fig. 3. (a) Linear absorption spectra of complexes 1-3 (8.8×10−5 mol/L) in CH2Cl2/CH3OH (8∶2) in a 2 mm cell, (b) triplet transient difference absorption (TA) spectra of 2 (2.39×10−5 mol/L) and 3 (2.09×10−5 mol/L) in a 1-cm cell. The TA spectrum of 1 was similar to that of 2, thus was not shown in Fig.3(b), (c) Z-scan experimental data and fitting curve for 3 in CH2Cl2/CH3OH (8∶2) with a concentration of 3×10−4 mol/L and a linear transmission of 95% at 532 nm in a 1 mm cell. Figures a and b are modified from Ref. [50] with permission, copyright © American Institute of Physics
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图 4.
Fig. 4. (a) and (b) Linear absorption spectra of complexes 4-12 (1×10−5 mol/L) in acetonitrile in a 1 cm cuvette, (c) ns TA spectra of 4, 5, 6 and 10 in acetonitrile in a 1 cm cell (A = 0.4 at 355 nm). See Ref. [51] for the ns TA spectra of 11 and 12 in acetonitrile, (d) time-resolved fs TA spectra of 11 in acetonitrile, (e) optical limiting curves of 4, 5, 10, 11 and 12 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% in the 2 mm cell. Figures are modified from Refs. [51] and [52] with permission, copyright © Chinese Optical Society and American Chemical Society, respectively
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图 5.
Fig. 5. (a) Linear absorption spectra of 19-22 (2.0×10−5 mol/L) in acetonitrile in a 1 cm cuvette, (b) ns TA spectra of 19-22 in acetonitrile in a 1 cm cell (A= 0.4 at 355 nm), (c) optical limiting curves of 19-22 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% at 532 nm in the 2 mm cell. Figures are modified from Ref. [53] with permission, copyright © American Chemical Society
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图 6.
Fig. 6. Structures of Pt(N^N^N) complexes 23-32
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图 7.
Fig. 7. (a) Linear absorption spectra of 23-27 in CH2Cl2, (b) ns time-resolved TA spectra of 25 in CH2Cl2 in a 1 cm cell (6.2×10−5 mol/L (A355 = 0.888)), (c) ns time-resolved TA spectra of 26 in CH2Cl2 in a 1 cm cell (3.9×10−5 mol/L (A355 = 0.564)), (d) optical limiting curves of 25-27 in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% at 532 nm in the 2 mm cell. 25 and 26 were dissolved in CH2Cl2, and 27 was dissolved in DMF. Figures are modified from Ref. [5] with permission, copyright © American Chemical Society
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图 8.
Fig. 8. (a) Linear absorption spectra of 28-32 in acetonitrile, (b) ns TA spectra of 28-32 in acetonitrile in a 1 cm cell (λex = 355 nm), (c) optical limiting curves of 28-32 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 75% at 532 nm in the 2 mm cell. Figures are modified from Ref.[56] with permission, copyright © American Chemical Society
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图 9.
Fig. 9. Structures of Pt(II) R-fluorenylterpyridine chloride complexes 33-37
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图 10.
Fig. 10. (a) UV-vis absorption spectra in CH3CN for 33-35, (b) time-resolved fs transient difference absorption spectra of 33 in CH3CN, (c) open-aperture Z-scan experimental data and fitting curve for 34 in CH3CN at 740 nm. The energy used for the experiment was 6.6 μJ, and the beam waist at the focal point was 31 μm. Figures are modified from Ref.[67] with permission, copyright © Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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图 11.
Fig. 11. (a) UV-vis absorption spectra of 36 and 37 in DMSO, (b) nanosecond TA spectra of 36 and 37 in CH3CN immediately after laser excitation. λex = 355 nm. A355 = 0.4 in a 1 cm cuvette. (c) optical limiting curves of 36 and 37 in DMSO solution for 4.1 ns laser pulses at 532 nm. The linear transmission of the solution was adjusted to 95% in a 2 mm cuvette. The beam waist at the focal plane was 72 μm, (d) wavelength dispersion of the ratios of excited-state absorption cross section to that of the ground-state absorption (σex/σ0) and TPA cross section (σ2) for 36 and 37 in DMSO solution. Figures are modified from Ref.[72] with permission, copyright © American Chemical Society
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图 12.
Fig. 12. Structures of mononuclear or multinuclear alkynylplatinum(Ⅱ) terpyridine complexes 38-44
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图 13.
Fig. 13. Structures of a trinuclear RuPt2 and heptanuclear RuPt6 complexes 45 and 46
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表 1Optical limiting parameters at 532 nm for ns laser pulsesa
Table1. Optical limiting parameters at 532 nm for ns laser pulsesa
| Complexes | Fth/J·cm−2 | Fthroughput/J·cm−2 | Tlim(at 3.6 J·cm−2)
| | aModified from Ref. [50] with permission. Copyright © American Institute of Physics
| | 1 | 0.03 | 1.07 | 0.30 | | 2 | 0.03 | 1.16 | 0.32 | | 3 | 0.02 | 0.45 | 0.12 |
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表 2Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile[51,53]
Table2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile[51,53]
| Complexes | τT/ns
| σ0c/10−19cm2 | Fthd/mJ·cm-2 | Tlime | σeff/σ0 | | aTriplet excited-state lifetime deduced from the decay of the TA at 700 nm, from Ref.[51]. bTriplet excited-state lifetime deduced from the decay of the TA at 680 nm, from Ref.[53]. cGround-state absorption cross section at 532 nm, from Refs. [51], [53] or [57].dRSA threshold when the transmission dropped to 90% of the linear transmission. eNonlinear transmittance at high incident fluence. fAt incident fluence of 2.5 J/cm2. gAt incident fluence of 3.0 J/cm2. This table is modified from Refs.[51] and [53] with permission. Copyrights © Chinese Optical Society and American Chemical Society, respectively
| | 4 | 766a | 2.43 | 48 | 0.28f, 0.25g | >3.57f, >3.89 g | | 5 | 659a | 7.18 | 144 | 0.34f | >3.02f | | 10 | 672a | 11.2 | 1090 | 0.44f | >2.30f | | 11 | 62a | 2.50[57] | 62 | 0.19f | >4.66f | | 12 | 51a | 2.40 | 900 | 0.45f | >2.24f | | 19 | 255b | 18.1 | 250 | 0.27g | >3.67g | | 20 | 408b | 4.30 | 370 | 0.27g | >3.67g | | 21 | 384b | 17.6 | 490 | 0.32g | >3.19g | | 22 | 2540b | 13.4 | 52 | 0.18g | >4.81g |
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表 3Photophysical parameters of 28-32 in CH3CN
Table3. Photophysical parameters of 28-32 in CH3CN
| 28 | 29 | 30 | 31 | 32 | | a 1MLCT/1LLCT band maxima. bFemtosecond (fs) TA band maxima. cSinglet excited-state lifetimes. dNanosecond (ns) TA band maxima. eTriplet excited-state lifetimes. fQuantum yields of the triplet excited-state formation. gIntersystem crossing (ISC) time. Data in rows 2 and 5-7 are from Ref. 56; data in rows 3, 4 and 8 are from Ref.[63], copyright © American Chemical Society and Old City Publishing, Inc., respectively
| | λabs/nma | 463 | 436 | 456 | 463 | 470 | | λS1-Sn/nmb | 717 | 685 | 712 | 719 | 766 | | τs/psc | 37±23 | 56±17 | 139±128 | 42±8 | 46±16 | | λT1-Tn/nmd | 725 | 720 | 755 | 730 | 785 | | τT/nse | 420 | 660 | 130 | 340 | 130 | | ΦTf | 0.65 | 0.53 | 0.19 | 0.64 | 0.66 | | τisc/psg | 57 | 106 | 732 | 66 | 70 |
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表 4Ground-state and excited-state absorption cross sections of 28-32 in CH3CN at 532 nm
Table4. Ground-state and excited-state absorption cross sections of 28-32 in CH3CN at 532 nm
| σ0a/10−18 cm2 | σTb/10−18 cm2 | σT/σ0 | σTΦT/σ0 | σsc/10−18 cm2 | σs/σ0 | σTd/10−17 cm2 | σT/σ0 | | aGround-state absorption cross-section. bTriplet excited-state absorption cross section deduced from the TA spectrum. cSinglet excited-state absorption cross sections obtained from fitting the Z-scan data. dTriplet excited-state absorption cross sections obtained from fitting the Z-scan data. Data in columns 2-5 are from Ref.[56]; while data in columns 6-9 are from Ref.[63], copyright © American Chemical Society and Old City Publishing, Inc., respectively
| | 28 | 1.30 | 60.1 | 46.2 | 30.0 | 32±2 | 29.2 | 12±2 | 9.2 | | 29 | 1.07 | 60.9 | 56.9 | 30.2 | 28±2 | 26.2 | 12±1 | 11.2 | | 30 | 1.53 | 160 | 104.5 | 19.9 | 18±1 | 11.8 | 14±2 | 9.2 | | 31 | 1.69 | 57.2 | 33.8 | 21.6 | 50±5 | 29.8 | 11±1 | 6.5 | | 32 | 4.60 | 45.4 | 9.9 | 6.5 | 30±2 | 6.5 | 13±2 | 2.8 |
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表 5Singlet excited-state absorption cross sections of 28 at different wavelengthsa
Table5. Singlet excited-state absorption cross sections of 28 at different wavelengthsa
| λ/nm
| σ0/10−18 cm2 | σs/10−18 cm2 | σs/σ0 | | aObtained from the best-fit of ps Z-scan data, reported in Ref.[63]. Copyright © Old City Publishing, Inc
| | 500 | 9.18 | 17.5±0.5 | 1.9 | | 532 | 1.30 | 38±2 | 29.2 | | 550 | 0.709 | 27±1 | 38.1 | | 570 | 0.302 | 15±2 | 49.7 | | 600 | 0.096 | 25±2 | 260.4 |
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表 6Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH3CN
Table6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH3CN
| Complex | λ/nm
| σ0 /cm2a | σS /10−18 cm2b | σS/σ0 | σ2 /GM
| | aGround-state absorption cross sections. bEffective singlet excited-state absorption cross sections with the assumption of σS2 = σS. cEstimated from the fs TA data at zero time delay. dσS2 = (12±7)×10−18 cm2. This table is modified from Ref.[67] with permission, copyright © Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
| | 33 | 575 | 10.1 | 20±1 | 2.0 | | | 600 | 3.83 | 20±2 | 5.2 | | | 630 | 0.956 | 17±1 | 18 | | | 670 | 0.191 | 25±1 | 131 | | | 740 | | 24.4c | | 850±50 | | 34 | 550 | 14.7 | 38±2 | 2.6 | | | 575 | 6.31 | 24±2 | 3.8 | | | 600 | 2.49 | 24±2 | 9.6 | | | 630 | 0.765 | 26±2 | 34 | | | 680 | 0.153 | 12±1 | 78 | | | 740 | | 7.7c | | 1 200±100 | | 760 | | 11.1c | | 1 000±200 | | 800 | | 7.7c | | 2 000±200 | | 825 | | 11.6c | | 600±100 | | 35 | 575 | 25.8 | 43±5d | 1.7 | | | 600 | 10.9 | 36±2 | 3.3 | | | 630 | 3.63 | 20±2 | 5.5 | | | 670 | 0.765 | 16±1 | 21 | |
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表 7Photophysical parameters of 36 and 37a
Table7. Photophysical parameters of 36 and 37a
| λabs/nm (ε/L·mol−1·cm−1) b | λS1-Sn/nm (τS/ps) b | λT1-Tn/nm (ε/L·mol−1·cm−1; τT/μs; ΦT) c | | aThis table is modified from Ref.[72] with permission, copyright © American Chemical Society. bIn DMSO. cIn CH3CN
| | 36 | 340 (32550), 378 (20200), 428 (26900) | 542 (49.4±18.3) | 530 (48560; 3.37; 0.72) | | 37 | 345 (39140), 385 (sh. 20140), 433 (27040) | 555 (58.7±25.4) | 545 (46150; 1.72; 0.58) |
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表 8Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data
Table8. Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data
| λ/nm
| σ0(λ)a/10−18 cm2 | σS(λ)/10−18 cm2 | σT(λ)c/10−18 cm2 | σS/σ0 | σT/σ0 | σ2(λ)/GM
| | 36 | 37 | 36 | 37 | 36 | 37 | 36 | 37 | 36 | 37 | 36 | 37 | | a Deduced from UV-Vis absorption spectrum. b Estimated from σS(532 nm) and the femtosecond transient difference absorption spectrum at zero time delay. These values are effective cross sections for the singlet excited states because the fs TA includes contributions from both S1 and S2 states. cσT(532 nm) was determined from the combined fitting of nanosecond and picosecond Z-scan data. For other wavelengths, σT(λ) was estimated from σT(532 nm) and the femtosecond transient difference absorption spectrum at 5.9 ns time delay. d Effective TPA cross sections for excited-state-assisted TPA. e Effective TPA cross section for the Z-scan of lowest energy (11.5 µJ at 825 nm, 7.9 µJ at 850 nm, 8.3 µJ at 875 nm, and 10.0 µJ at 900 nm). This table is modified from Ref.[72] with permission, copyright © American Chemical Society
| | 480 | 5.23 | − | 28 | − | 28 | − | 5.35 | − | 5.35 | − | − | − | | 500 | 1.41 | 1.32 | 22 | 42 | 40 | 14 | 15.6 | 31.8 | 28.4 | 10.6 | − | − | | 532 | 0.0955 | 0.390 | 42 | 19 | 68 | 21 | 440 | 48.7 | 712 | 53.8 | − | − | | 550 | 0.0435 | 0.187 | 35 | 35 | 66 | 28 | 805 | 187 | 1517 | 150 | − | − | | 600 | 0.0222 | 0.0726 | 21b | 40 | 29 | 15 | 946 | 551 | 1306 | 207 | 50 | − | | 630 | 0.0076 | 0.0336 | 17b | 29b | 23 | 13 | 2237 | 863 | 3026 | 387 | 110 | 1500 | | 680 | ~0 | 0.0153 | 19b | 27b | 23 | 13 | −1765 | | − | 850 | 160 | 600 | | 740 | ~0 | 0.0084 | 22b | 28b | 31 | 15 | −3333 | | −1786 | | 65 | 550 | | 760 | ~0 | ~0 | 22b | 29b | 36 | 16 | − | − | − | − | 90 | 400 | | 800 | ~0 | ~0 | 22b | 23b | 53 | 20 | − | − | − | − | 60 | 450 | | 825 | ~0 | ~0 | − | 43b | − | 21 | − | − | − | − | 200d | 500 | | 850 | ~0 | ~0 | − | − | − | − | − | − | − | − | 280d | 3700e | | 875 | ~0 | ~0 | − | − | − | − | − | − | − | − | 180d | 3000e | | 900 | ~0 | − | − | − | − | − | − | − | − | − | 200d | − | | 910 | ~0 | ~0 | − | − | − | − | − | − | − | − | − | 1700e |
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孙文芳. 联三吡啶铂(Ⅱ)配合物的非线性吸收和光限幅（特邀）[J]. 红外与激光工程, 2020, 49(12): 20201078. Wenfang Sun. Nonlinear absorption and optical limiting of platinum(Ⅱ) terpyridine complexes (Invited)[J]. Infrared and Laser Engineering, 2020, 49(12): 20201078.
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