Two heteroleptic monocationic Ir( iii ) complexes bearing 6,6′-bis(7-benzothiazolylfluoren-2-yl)-2,2′-biquinoline as the diimine ligand with different degrees of π-conjugation were synthesized and their photophysics was investigated by spectroscopic techniques and first principles calculations. These complexes possessed two intense absorption bands at 300–380 nm and 380–520 nm in toluene that are predominantly ascribed to the diimine ligand-localized 1 π,π* transition and intraligand charge transfer ( 1 ILCT)/ 1 π,π* transitions, respectively, with the latter being mixed with minor 1 MLCT (metal-to-ligand charge transfer)/ 1 LLCT (ligand-to-ligand charge transfer) configurations. Both complexes also exhibited a spin-forbidden, very weak 3 MLCT/ 3 LLCT/ 3 π,π* absorption band at 520–650 nm. The emission of these complexes appeared in the red spectral region ( λ em : 640 nm for Ir-1 and 648 nm for Ir-2 in toluene) with a quantum yield of <10% and a lifetime of hundreds of ns, which emanated from the 3 ILCT/ 3 π,π* state. The 3 ILCT/ 3 π,π* state also gave rise to broad and moderately strong transient absorption (TA) at ca. 480–800 nm. Extending the π-conjugation of the diimine ligand via inserting CC triplet bonds between the 7-benzothiazolylfluoren-2-yl substituents and 2,2′-biquinoline slightly red-shifted the absorption bands, the emission bands, and the TA bands in Ir-2 compared to those in Ir-1 that lacks the connecting CC triplet bonds in the diimine ligand. The stronger excited-state absorption with respect to the ground-state absorption at 532 nm led to strong reverse saturable absorption (RSA) for ns laser pulses at this wavelength, with the RSA of Ir-2 being slightly stronger than that of Ir-1, which correlated well with their ratios of the excited-state to ground-state absorption cross sections ( σ ex / σ 0 ). These results suggest that extending the π-conjugation of the 2,2′-biquinoline ligand via incorporating the 7-benzothiazolylfluoren-2-yl substituents retained the broad but weak ground-state absorption at 500–650 nm, meanwhile increased the triplet excited-state lifetimes, which resulted in the much stronger triplet excited-state absorption in this spectral region and strong RSA at 532 nm. Thus, these complexes are promising candidates as broadband reverse saturable absorbers.
more »
« less
The effect of CO rotation from shaped pulse polarization on reactions that form C 2
The effect of CO rotational energy on bimolecular reactions to form electronically excited C 2 is reported here. The reactions are initiated by CO multiphoton absorption of 800 nm light in strong optical fields using two different polarization configurations based on shaped chirped pulses. The observation of Swan band emission indicates that C 2 (d 3 Π g ) is a reaction product. The optical polarization is in the form of either an optical centrifuge or a dynamic polarization grating. In each case, the strong field aligns CO molecules and induces multiphoton absorption. Power-dependent measurements indicate at least seven photons are absorbed by CO; CO(a 3 Π) is a likely reactant candidate based on kinetic modeling. Relative reaction efficiencies are determined by measuring Swan band emission intensities. For a CO pressure of 100 Torr and an optical intensity of I = 2.0 × 10 13 W cm −2 , the relative C 2 (d 3 Π g ) yield with the dynamic polarization grating is twice that with the optical centrifuge. The extent of CO rotational energy was determined for both optical polarizations using high-resolution transient IR absorption for a number of CO states with J = 62–73 and E rot up to 10 400 cm −1 . Optical centrifuge excitation generates at least 2.5 times more rotationally excited CO molecules per quantum state than the dynamic polarization grating. The results indicate that the effect of large amounts of CO rotational energy is to reduce the yield of the C 2 products.
more »
« less
- Award ID(s):
- 1800531
- PAR ID:
- 10112631
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 21
- Issue:
- 26
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 14103 to 14110
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
This paper presents an extensive parameter study of a non-intrusive and non-seeded laser diagnostic method for measuring one dimensional (1D) rotational temperature of molecular nitrogen (N2) at 165 - 450 K. Compared to previous efforts using molecular oxygen, here resonantly ionized and photoelectron induced fluorescence of molecular nitrogen for thermometry (N2RIPT) was demonstrated. The RIPT signal is generated by directly probing various rotational levels within the rovibrational absorption band of N2, corresponding to the 3-photon transition of N2(
X 1Σg +,v =0→b 1Πu ,v ′=6) near 285 nm, without involving collisional effects of molecular oxygen and nitrogen. The photoionized N2produces strong first negative band of N2+(B 2Σu +−X 2Σg +) near 390 nm, 420 nm, and 425 nm. Boltzmann analyses of various discrete fluorescence emission lines yield rotational temperatures of molecular nitrogen. By empirically choosing multiple rotational levels within the absorption band, non-scanning thermometry can be accurately achieved for molecular nitrogen. It is demonstrated that the N2RIPT technique can measure 1D temperature profile up to ∼5 cm in length within a pure N2environment. Multiple wavelengths are thoroughly analyzed and listed that are accurate for RIPT for various temperature ranges. -
A combined experimental and theoretical study of quantum state-resolved rotational energy transfer kinetics of optically centrifuged CO molecules is presented. In the experiments, inverted rotational distributions of CO in rotational states up to J=80 were prepared using two different optical centrifuge traps, one with the full spectral bandwidth of the optical centrifuge pulses, and one with reduced bandwidth. The relaxation kinetics of the high-J tail of the inverted distribution from each optical trap was determined based on high-resolution transient IR absorption measurements. In parallel studies, master equation simulations were performed using state-to-state rate constants for CO-CO collisions in states up to J=90, based on data from double-resonance experiments for CO with J=0-29 and a fit to a statistical power exponential gap model. The model is in qualitative agreement with the observed relaxation profiles, but the observed decay rate constants are smaller than the simulated values by as much as a factor of 10. The observed decay rate constants also have a stronger J-dependence than predicted by the model. The results are discussed in terms of angular momentum and energy conservation, and compared to the observed orientational anisotropy decay kinetics of optically centrifuged CO molecules. Models for rotational energy transfer could be improved by including angular momentum effects.more » « less
-
more » « less
We report the experimental resonance enhanced multiphoton ionization spectrum of isoquinoline between 315 and 310 nm, along with correlated electronic structure calculations on the ground and excited states of this species. This spectral region spans the origin transitions to a π–π* excited state, which previous work has suggested to be vibronically coupled with a lower lying singlet n–π* state. Our computational results corroborate previous density functional theory calculations that predict the vertical excitation energy for the n–π* state to be higher than the π–π* state; however, we find an increase in the C–N–C angle brings the n–π* state below the energy of the π–π* state. The calculations find two out-of-plane vibrational modes of the n–π* state, which may be brought into near resonance with the π–π* state as the C–N–C bond angle increases. Therefore, the C–N–C bond angle may be important in activating vibronic coupling between the states. We fit the experimental rotational contour with a genetic algorithm to determine the excited state rotational constants and orientation of the transition dipole moment. The fits show a mostly in-plane polarized transition, and the projection of the transition dipole moment in the a-b plane is about 84° away from the a axis. These results are consistent with the prediction of our electronic structure calculations for the transition dipole moment of the π–π* excited state.
-
State-to-state rotational energy transfer in collisions of ground ro-vibrational state 13 CO molecules with N 2 molecules has been studied using the crossed molecular beam method under kinematically equivalent conditions used for 13 CO + CO rotationally inelastic scattering described in a previously published report (Sun et al. , Science , 2020, 369 , 307–309). The collisionally excited 13 CO molecule products are detected by the same (1 + 1′ + 1′′) VUV (Vacuum Ultra-Violet) resonance enhanced multiphoton ionization scheme coupled with velocity map ion imaging. We present differential cross sections and scattering angle resolved rotational angular momentum alignment moments extracted from experimentally measured 13 CO + N 2 scattering images and compare them with theoretical predictions from quasi-classical trajectories (QCT) on a newly calculated 13 CO–N 2 potential energy surface (PES). Good agreement between experiment and theory is found, which confirms the accuracy of the 13 CO–N 2 potential energy surface for the 1460 cm −1 collision energy studied by experiment. Experimental results for 13 CO + N 2 are compared with those for 13 CO + CO collisions. The angle-resolved product rotational angular momentum alignment moments for the two scattering systems are very similar, which indicates that the collision induced alignment dynamics observed for both systems are dominated by a hard-shell nature. However, compared to the 13 CO + CO measurements, the primary rainbow maximum in the DCSs for 13 CO + N 2 is peaked consistently at more backward scattering angles and the secondary maximum becomes much less obvious, implying that the 13 CO–N 2 PES is less anisotropic. In addition, a forward scattering component with high rotational excitation seen for 13 CO + CO does not appear for 13 CO–N 2 in the experiment and is not predicted by QCT theory. Some of these differences in collision dynamics behaviour can be predicted by a comparison between the properties of the PESs for the two systems. More specific behaviour is also predicted from analysis of the dependence on the relative collision geometry of 13 CO + N 2 trajectories compared to 13 CO + CO trajectories, which shows the special ‘do-si-do’ pathway invoked for 13 CO + CO is not effective for 13 CO + N 2 collisions.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8cp06917d
