New Insights To Simulate the Luminescence Properties of Pt(II

Article pubs.acs.org/JCTC

New Insights To Simulate the Luminescence Properties of Pt(II) Complexes Using Quantum Calculations Florian Massuyeau,* Eric Faulques, and Camille Latouche* Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes cedex 3, France S Supporting Information *

ABSTRACT: The present manuscript reports a thorough quantum investigation on the luminescence properties of three monoplatinum(II) complexes. First, the simulated bond lengths at the ground state are compared to the observed ones, and the simulated electronic transitions are compared to the reported ones in the literature in order to assess our methodology. In a second time we show that geometries from the first triplet excited state are similar to the ground state ones. Simulations of the phosphorescence spectra from the first triplet excited states have been performed taking into account the vibronic coupling effects together with modemixing (Dushinsky) and solvent effects. Our simulations are compared with the observed ones already reported in the literature and are in good agreement. The calculations demonstrate that the normal modes of low energy are of great importance on the phosphorescence signature. When temperature effects are taken into account, the simulated phosphorescence spectra are drastically improved. An analysis of the computational time shows that the vibronic coupling simulation is cost-effective and thus can be extended to treat large transition metal complexes. In addition to the intrinsic importance of the investigated targets, this work provides a robust method to simulate phosphorescence spectra and to increase the duality experiment-theory.

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INTRODUCTION In the past years, compounds with a strong emission in the entire visible range have been thoroughly investigated in order to develop new devices such as light-emitting cells (LEC) or organic light-emitting diodes (OLED) based systems.1−3 Among all possible targets, Ru(II) complexes associated with polypyridine ligands are probably the most studied inorganic transition metal complexes due to their remarkable capability to phosphoresce in this region. However, one of the main drawbacks of such candidates comes from their very low quantum yield which constitutes a lock to new applications.3−15 Therefore, chemists have started to investigate new transition metal complexes to tackle this issue.16−19 Platinum(II) complexes sound promising targets thanks to their strong and tunable phosphorescence in almost the whole visible range.20−25 There are several ways to modulate the emission wavelength of the platinum(II) complexes. First, one can decrease the LUMO or raise the HOMO energies.20,26 Second, one may tune the HOMO−LUMO gap by modifying the interand intraligand conjugation.27−29 Third, one can add a new metallic center.30−32 Recently, a combined theoretical and experimental work with molecules based on Pt(II) complexes with triarylborane (TAB)-conjugated acetylacetone (acacH) and with a tunable cyclometalate ligand showed a very nice phosphorescence modulation.33 Indeed, with the substitution of the 2-phenylpyridine by the 2-thiophenylpyridine or by the 2© 2017 American Chemical Society

thianapthenylpyridine, the emission wavelength in solution (CH2Cl2) rose from ca. 480 to 600 nm. This paper also demonstrates that the modulation of the TAB, by addition of methyl groups on the phenyl linking the TAB and acacH moieties, solely enhances the quantum yield. The capability of these recently published compounds to emit in a large range with a large number of different atoms (H, B, C, N, O, S, Pt) prompted us to test the robustness of our computational strategy. It is also an opportunity to offer to a wide range of scientists a straightforward protocol to explore new targets for designing optical based devices. From a computational point of view, it remains very challenging to simulate phosphorescence spectra for transition metal complexes, especially if one tries to introduce a large number of parameters such as mode-mixing, solvent, and temperature effects. Recently, Barone et al. have provided many contributions in this field.34−41Among them, the authors showed that using the B3PW91 functional with LANL2DZ basis set provides a reliable, cheap in time consumption and powerful set of computations to achieve the reproduction of the phosphorescence signature of transition metal complexes including ruthenium, iridium, and platinum.40−44 Received: January 31, 2017 Published: March 13, 2017 1748

DOI: 10.1021/acs.jctc.7b00103 J. Chem. Theory Comput. 2017, 13, 1748−1755

Journal of Chemical Theory and Computation

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RESULTS AND DISCUSSION Ground-State Geometric Structures. First, the geometric parameters of the GS of the simulated data are compared with the available experimental ones obtained by X-ray scattering. The X-ray structure of the complex 1 was not provided. Therefore, we compared our results with the structural parameters of the complex 2 available in ref 33 which is very similar to the complex 1. Indeed, the difference between 1 and 2 concerns the linking phenyl where terminal moieties are H for 1 and Me for 2. The averaged Pt−O distances from our simulations fit nicely the observed ones. Data provided in ref 33 demonstrates that the Pt−N distances are smaller than the Pt− O ones by ≃0.1 Å (Table 1). This is also the case in our

In this paper, we report a full quantum investigation of three platinum(II) complexes based on DFT methods (Scheme 1). Scheme 1. Investigated Metal Complexesa

a

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Table 1. Theoretical and Experimental (between Brackets) Relevant Geometric Data

Numeration is kept as in ref 33 for clarity. Adapted from ref 33.

1 (2)a

These complexes have been chosen as targets because their experimental photoluminescence ranges between the blue, the green, and the orange colors. After a brief exploration of the ground state (GS) characteristics, we focus our attention on the triplet excited states (ES) and propose a strategy to simulate accurately the phosphorescence spectra of the three platinum(II) complexes. We also provide new insights concerning vibrations involved in the luminescence signature, and we also performed computations using temperature effects. Finally, an analysis of this computational protocol and its time consumption is proposed.

Pt−O av (Å) Pt−N (Å) Pt−C (Å) B−C av (Å) a

2.072 1.993 1.962 1.567

(2.036) (1.960) (1.979) (1.626)

3 (3)a 2.064 2.007 1.958 1.566

(2.026) (1.911) (1.968) (1.571)

Labels of the reference paper in ref 33.

computations. The simulated Pt−C distances are also in good agreement with the observed ones. On average, the square planar ML4 stereochemistry is nicely reproduced in our computations. Finally, the B−C distances are also well modeled. Ground-State Electronic Structures and Electronic Vertical Excitations. As the electronic structure and the band assignments have already been investigated by Thilagar and Kumar, these aspects are herein briefly discussed.33 In order to evaluate our computational protocol, electronic excitations have been computed using the TD-DFT method on the optimized geometries. As one can see in Figure 1, the simulated spectra of the complexes 1, 3, and 5 fit reasonably the experimental ones.33 One should notice that the longest wavelength excitations implying the first excited state, and thus often leading to the observed luminescence properties, is nicely reproduced in our simulations with respect to experimental data. However, it is important to mention that the agreement between experiment and theory slightly decreases for highest energies. The slight redshift of the highest excitation wavelength when going from the complex 1 to the complex 5 is respected in our computations. Indeed, the lowest energy excitations are computed at 3.21, 3.10, and 2.87 eV for, respectively, the complexes 1, 3, and 5. For the complexes 1 and 3, these excitations correspond to the transition from the HOMO and the HOMO−1 to the LUMO and the LUMO+1. For the complex 5, the excitation is assigned as a HOMO to LUMO and LUMO+1 transition. Very intense transitions appear around 3.4 eV for the three complexes. For the complex 1, there is only one computed intense excitation occurring at 3.37 eV. This excitation corresponds to the transition from the HOMO and the HOMO−1 to the LUMO, the LUMO+1, and the LUMO+2. For the complexes 3 and 5, according to our calculations, two transitions show up in this region. For the complex 3, they appear at 3.36 and 3.48 eV. These transitions are similar to those of the complex 1. For the complex 5, the excitations are computed at 3.39 and 3.58 eV. The one of lowest energy can be assigned to a

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COMPUTATIONAL DETAILS All calculations have been performed at the DFT level of theory employing the G09D01 suite of programs.45 On the basis of several previous studies,15,32,42 the B3PW91 functional to perform the computations has been chosen.46−48 The associated basis set is the so-called LANL2DZ, including a pseudopotential for inner electrons of Pt and augmented with polarization functions on B (d; 0.500), C(d; 0.587), N(d; 0.736), O(d; 0.961), S(d; 0.55), and Pt(f; 0.8018).49−52 Solvent effects (CH2Cl2) have been taken into account by the Polarizable Continuum Model (PCM).53,54 All the GS and ES geometries have been optimized and checked to be true minima on the Potential Energy Surface (PES) by diagonalizing their Hessians. Time-Dependent Density Functional Theory (TD-DFT) computations have been performed, using the optimized ground state geometries, to obtain excitations energies and spectra. In order to plot the phosphorescence spectra, vibronic contributions to electronic emission have been considered using the Adiabatic Hessian (AH) approach as implemented in the used version of the Gaussian Package.34,35 The AH model allows the inclusion of the mode-mixing effects upon a decent treatment of the potential energy surfaces of both GS and ES. The model could be improved by including anharmonic effects. A complete anharmonic treatment (including intensity) was out of the question because of the excessive computational cost. In order to reach a sufficient spectrum progression, methyl groups have been substituted by hydrogens. To obtain a better description of the phosphorescence spectra, temperature effects have been taken into account. The optimized geometries and vibrational frequencies of the first triplet states have been obtained using unrestricted calculations. The simulated phosphorescence spectra have been plotted using the VMS programs.38 1749


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Figure 2. Differences of geometry between the initial (yellow) and the final (blue) states of 1, 3, and 5.

and Pt−C bond lengths. Finally, it must be pointed out that the B−C bonds are barely affected by the change of state (Table 2). These results gave us confidence in order to include the vibrational contributions to the electronic transitions to simulate the luminescence (phosphorescence) spectra.

Figure 1. Simulated electronic spectra of the complexes 1 (blue), 3 (green), and 5 (red), numerized experimental spectra are in black (intensity in a.u., recorded in N2 according to ref 33).

Table 2. Relevant Geometric Parameters of Complexes 1, 3, and 5 1

HOMO−1 to LUMO transition due to its strong majority (∼90%). The second is also dominated by the HOMO−1 to the LUMO+1 transition (∼80%), whereas a non-negligible HOMO to LUMO+3 transition (∼10%) is computed. The other absorption bands are more mixed and will not be discussed in the present paper. It is also important to mention that the computed transitions are similar to the previously reported ones.33 Even though these results were expected, this trend provided us confidence in our computational protocol concerning the ground state, especially concerning the lowest energy transition. In the next section, the structural and optical properties issuing from the triplet excited state are detailed. Triplet Excited-State Structures and Properties. The triplet ES of all complexes were investigated using the so-called unrestricted method,55 where α and β spins are separately treated with a spin multiplicity equal to 3. The nature (minimum) of the relaxed geometries has been checked with no imaginary frequency. In this section the geometrical differences between the GS and ES are discussed for all complexes. Indeed, if one wants to use the vibronic coupling model explained in the Computational Details section, the geometries of the initial and final states have to be close. As one can see in Figure 2 the geometries of the GS and the ES are similar. Furthermore, the dihedral angles and the bond-lengths are almost the same when going from the initial state to the final state. However, it is important to mention that coming from the GS to the ES there is a constant shortening of the Pt−N

Pt−O av (Å) Pt−N (Å) Pt−C (Å) B−C av (Å)

3

5

GS

ES

GS

ES

GS

ES

2.072 1.993 1.962 1.567

2.046 1.986 1.933 1.568

2.064 2.007 1.958 1.566

2.069 1.993 1.929 1.567

2.059 2.003 1.972 1.567

2.068 1.995 1.939 1.567

On these grounds, phosphorescence spectra have been simulated for all studied complexes. Great care has been taken to get vibronic progressions above 90%. This value of 90% permits us to be confident concerning the reliability of the vibronic progression. In Figure 3 are reported the simulated and the observed phosphorescence spectra. As one can see the simulations fit nicely the experimental records.33 For the complex 1 (blue), the simulated spectrum agrees with the experimental one and is constituted by a maximum, two shoulders and a tail. The shoulders are respectively at ∼0.2 and 0.4 eV lower in energy than the maximum. It is also important to mention that if one applies a small shift on the simulated spectra, in such a way that both observed and simulated maxima are superposed, the shoulders are in the good range of energy with respect to experiment. The case of complex 3 is more complicated. Experimentally, the maximum appears around 2.3 eV, then a strong decrease of intensity with a hill at 2.2 eV and an intense shoulder at 2.1 eV to finish with one shoulder at 1.9 eV. As a matter of fact, it appears that our simulated spectrum reproduces almost completely the observed one, despite an 1750


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but with a non-negligible rocking character of the phenyl rings around the Pt and B atoms. The shift-vectors for complexes 3 and 5 look similar but differ from the complex 1. Indeed, in these cases there are more normal modes involved with an important shift-vector (Figure SI). This fact also explains why the simulated spectra of the complexes 3 and 5 possess a stronger vibrational signature than the complex 1. For the complex 3, the three normal modes with the stronger shift-vectors are described because they possess a factor of about two in comparison to the others. They correspond to the normal modes nos. 1, 5, and 57, respectively computed at 18, 47, and 709 cm−1. The two first ones are rather similar to the complex 1. However, the vibration no. 57 is exclusively localized on the C and H atoms of the two terminal phenyl groups. It can be approximated to a wagging motion of the two terminal phenyls linked to the B atom (Figure 4). However, it is important to mention that many normal modes with a nonnegligible shift-vector are involved in the entire vibrational range (Figure SI). For the complex 5, there are more than 20 normal modes which have a non-negligible shift-vector. As for the complex 3, it is herein only described the three most important, and they correspond to normal modes nos. 2, 28, and 119 with eigenvalues respectively computed at 16, 287, and 1192 cm−1. The normal mode no. 2 possesses a similar signature as for the complexes 1 and 3, averagely involving all the atoms in a rocking motion. The mode no. 28 is associated with a metallic character where the Pt atom is free to move along one direction of the square plane (stretching). This vibration can also be characterized by the rotation of the phenyl groups together with a C−S elongation. Finally the mode no. 119 corresponds to the C−H bending of the phenyl rings. However, whereas the trend for the intensities is nicely simulated, the relative values of the shoulders are overestimated in our simulations for the complexes 3 and 5. This last point prompted us to take into account the temperature effects in order to correct the relative intensities and get a more reliable model. Temperature Effects. In order to improve our reproduction, temperature effects have been taken into account as implemented in the Gaussian Package. Furthermore, to simulate the emission spectra in a reasonable time with temperature effects, the minimum ratio population (MinPop) state of a vibrational state to be taken into account as the starting point of a transition has been tuned. A more common definition could be the following: the percentage of a vibrational state that needs to be populated for it to be considered as the initial state of a transition. As one can see in Figures 5 and 6, the inclusion of temperature effects does not impact the energetic range of the luminescence signature but solely the intensities and thus actively modifies the shape of the simulated vibronic spectrum. As a matter of fact, the maximum becomes even more intense than the shoulders and the hills. Moreover, the tail of the complex 3, which is nicely recorded in the experimental spectrum, is now reproduced with the good intensity in our simulation. The simulated phosphorescence of the complex 5 is also in very good agreement with respect to experiments. All the recorded information on the observed spectrum is correctly reproduced in our simulation. In Figure 6 is displayed the evolution of the simulated phosphorescence spectrum of the complex 3 with respect to the inclusion of the

Figure 3. Simulated (plain) and experimental (dashed) phosphorescence spectra of 1, 3, and 5. The shifted simulated AH-FC (dashed) is moved to be at the maximum of the observed one.33

overestimation in intensity of the shoulders. The shoulders, the hill, and the maximum are all present. Furthermore, upon addition of the small shift (ca. 0.2 eV for all complexes), all the information is positioned with the good energies. The complex 5 exhibits a strong signature at 2.1 eV, a second intense band at 1.9 eV, and a weak shoulder around 1.6 eV. Once again, the AH|FC method reproduces quantitatively the spectrum. In order to characterize the normal modes involved in the electronic transition, the shift-vectors of all complexes were investigated. The shift-vector is described as the gradient of the final state projected onto the normal modes of the initial state.32 It turns out that for the complex 1, the normal modes no. 2 and no. 3 possess a shift-vector four times greater than the others (Figure SI). These normal modes are depicted in Figure 4. As one can see, the normal modes no. 2 (19 cm−1) and no. 3 (21 cm−1) correspond to the vibration of the whole molecule 1751


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Figure 4. Displacement of atoms associated with the normal modes with the largest shift-vectors. 1a and 1b, 3a, 3b, and 3c, and 5a, 5b, and 5c respectively correspond to normal modes 2 and 3 of the complex 1; normal modes 1, 5, and 57 of the complex 3; and normal modes 2, 28, and 119 of the complex 5.

temperature effects (with and without) and of the MinPop (0.3 to 0.6). Adding a MinPop of 0.6 slightly modifies the intensity of the band at 1.85 eV. Furthermore, with the inclusion of more population, i.e. decreasing the value of the MinPop, the intensities diminish dramatically. Finally, the best agreement is obtained enforcing a MinPop = 0.5 which represents also a computational effective choice (see later). These results demonstrate the strong importance to take into account the temperature effects in the models in order to get more reliable results. Analysis of the Time Consumption. In this section we briefly compare and analyze the computation cost of the vibronic treatment with and without temperature effects with respect to optimization+frequency calculations of the GS and the ES on the complex 3 (Figure 7). As displayed in Figure 7, the vibronic computation without temperature effects is very cheap and represents less than 1% of the ES computational time. With the inclusion of temperature effects to simulate the phosphorescence spectrum, the percentage of the vibronic calculation increases dramatically. Furthermore, based on our results, when one enforces a MinPop ranging from 0.5 to 0.6, the computational cost remains sufficiently weak to be used on a large set of molecules. Indeed, the time for the vibronic treatment is on the order of magnitude of the ES study which is the normalized value in Figure 7. However, it turned out that using MinPop = 0.3 or 0.4 considerably increases the computational cost of the vibronic procedure (∼80%), essentially due to the high number of states required in these computations. Finally, taking into account this evolution for the vibronic phosphorescence spectrum with MinPop = 0.2 would be very expensive and would probably represent more than ten times the total time consumption to investigate the ES.

Figure 5. Simulated phosphorescence spectra of complexes 3 and 5 without (dash) and with (plain square) temperature effects vs observed phosphorescence spectra (plain gray).

Figure 6. Evolution of the simulated phosphorescence spectrum of the complex 3 with respect to the temperature effects and to the MinPop.

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Journal of Chemical Theory and Computation ORCID

Camille Latouche: 0000-0002-3541-3417 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research used resources of CCIPL (Centre de Calcul Intensif des Pays de Loire). Prof. Vincenzo Barone (SNS Pisa, Italy), who made available the VMS package developed in his laboratory, is greatly acknowledged. C.L. thanks Prof. Emmanuel Fritsch for fruitful discussions.

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Figure 7. Evolution of the computational costs (ratio) with respect to the computation types: computations to study the GS, the ES, and the vibronic effects. Normalization has been performed on the computational time required to investigate the ES.

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CONCLUSION AND PERSPECTIVES From a computational viewpoint, it is now well established that the conjunction of the B3PW91 hybrid functional with the LANL2DZ+pol. basis set provides a good description of the GS and ES. 15,32,40,42,44 Indeed, the computational protocol proposed here demonstrates clearly its robustness for the vertical excitations and for the excited state and its optical properties, more specifically here the phosphorescence. The strong phosphorescence signature is nicely reproduced in our simulations and permitted us to rationalize the mechanisms originating with the optical signatures. From a chemical viewpoint, in this paper we have also provided new insights concerning platinum complexes and have underlined that the normal modes of low energy have a deep impact on the structure of the emission bands. This fact confirms the trend established by some of us in a previous paper on platinum complexes.32 The computational model used here is among the most possible refined. It properly takes into account the solvation regime, the mode-mixing between GS and ES, and the temperature effects. Nevertheless, some improvement could be performed especially if one takes properly into account the spin−orbit coupling.56−59It would allow the absolute intensity computations together with Herzberg−Teller effects. Another improvement should be the inclusion of anharmonic effects.60,61 However, a total treatment is out of consideration. Furthermore, these effects are expected to be rather small for this kind of spectroscopy, whereas, as an example, for the resonance Raman spectroscopy they are very strong.39,40 In the near future this kind of calculations could lead to the investigation of the luminescence properties at the solid state. A cluster approach has already been discussed on the S-doped sodalite.62

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jctc.7b00103. Shift-vectors of the three investigated complexes (PDF)

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REFERENCES

(1) D’Andrade, B. W.; Forrest, S. R. White Organic Light-Emitting Devices for Solid-State Lighting. Adv. Mater. 2004, 16 (18), 1585− 1595. (2) Sun, Y.; Forrest, S. R. High-Efficiency White Organic Light Emitting Devices with Three Separate Phosphorescent Emission Layers. Appl. Phys. Lett. 2007, 91 (26), 263503. (3) Chen, C.-Y.; Pootrakulchote, N.; Chen, M.-Y.; Moehl, T.; Tsai, H.-H.; Zakeeruddin, S. M.; Wu, C.-G.; Grätzel, M. A New Heteroleptic Ruthenium Sensitizer for Transparent Dye-Sensitized Solar Cells. Adv. Energy Mater. 2012, 2 (12), 1503−1509. (4) Schulze, M.; Steffen, A.; Würthner, F. Near-IR Phosphorescent Ruthenium(II) and Iridium(III) Perylene Bisimide Metal Complexes. Angew. Chem., Int. Ed. 2015, 54 (5), 1570−1573. (5) Lundqvist, M. J.; Galoppini, E.; Meyer, G. J.; Persson, P. Calculated Optoelectronic Properties of Ruthenium Tris-Bipyridine Dyes Containing Oligophenyleneethynylene Rigid Rod Linkers in Different Chemical Environments. J. Phys. Chem. A 2007, 111 (8), 1487−1497. (6) Chou, C.-C.; Hu, F.-C.; Yeh, H.-H.; Wu, H.-P.; Chi, Y.; Clifford, J. N.; Palomares, E.; Liu, S.-H.; Chou, P.-T.; Lee, G.-H. Highly Efficient Dye-Sensitized Solar Cells Based on Panchromatic Ruthenium Sensitizers with Quinolinylbipyridine Anchors. Angew. Chem., Int. Ed. 2014, 53 (1), 178−183. (7) Kinoshita, T.; Dy, J. T.; Uchida, S.; Kubo, T.; Segawa, H. Wideband Dye-Sensitized Solar Cells Employing a PhosphineCoordinated Ruthenium Sensitizer. Nat. Photonics 2013, 7 (7), 535− 539. (8) Heinze, K.; Hempel, K.; Tschierlei, S.; Schmitt, M.; Popp, J.; Rau, S. Resonance Raman Studies of Bis(terpyridine)ruthenium(II) Amino Acid Esters and Diesters. Eur. J. Inorg. Chem. 2009, 2009 (21), 3119− 3126. (9) Muhavini Wawire, C.; Jouvenot, D.; Loiseau, F.; Baudin, P.; Liatard, S.; Njenga, L.; Kamau, G. N.; Casida, M. E. DensityFunctional Study of Luminescence in Polypyridine Ruthenium Complexes. J. Photochem. Photobiol., A 2014, 276 (0), 8−15. (10) Bhuiyan, A. a.; Kincaid, J. R. Synthesis and Photophysical Properties of Zeolite-Entrapped Bisterpyridine Ruthenium(II). Dramatic Consequences of Ligand-Field-State Destabilization. Inorg. Chem. 1998, 37 (10), 2525−2530. (11) Basu, A.; Gafney, H. D.; Strekas, T. C. Resonance Raman Spectra of Ruthenium (II) Complexes of Bipyridine and Substituted Bipyridines: Ground-and Excited-State Properties. Inorg. Chem. 1982, 21 (12), 2231−2235. (12) Labat, F.; Ciofini, I.; Hratchian, H. P.; Frisch, M. J.; Raghavachari, K.; Adamo, C. Insights into Working Principles of Ruthenium Polypyridyl Dye-Sensitized Solar Cells from First Principles Modeling. J. Phys. Chem. C 2011, 115 (10), 4297−4306. (13) Gorelsky, S. I.; Lever, A. B. P. Electronic Structure and Spectra of Ruthenium Diimine Complexes by Density Functional Theory and INDO/S. Comparison of the Two Methods. J. Organomet. Chem. 2001, 635 (1−2), 187−196. (14) Guimaraes, R. R.; Parussulo, A. L. A.; Toma, H. E.; Araki, K. New Tunable Ruthenium Complex Dyes for TiO2 Solar Cells. Inorg. Chim. Acta 2013, 404 (0), 23−28.

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Article

Journal of Chemical Theory and Computation (15) Vazart, F.; Latouche, C. Validation of a Computational Protocol to Simulate near IR Phosphorescence Spectra for Ru(II) and Ir(III) Metal Complexes. Theor. Chem. Acc. 2015, 134 (12), 144. (16) Broeckx, L. E. E.; Delaunay, W.; Latouche, C.; Lutz, M.; Boucekkine, A.; Hissler, M.; Müller, C. C-H Activation of 2,4,6Triphenylphosphinine: Synthesis and Characterization of the First Homoleptic Phosphinine-iridium(III) Complex Fac-[Ir(Ĉ P)3]. Inorg. Chem. 2013, 52 (19), 10738−10740. (17) Dragonetti, C.; Colombo, A.; Marinotto, D.; Righetto, S.; Roberto, D.; Valore, A.; Escadeillas, M.; Guerchais, V.; Le Bozec, H.; Boucekkine, A.; et al. Functionalized Styryl Iridium (III) Complexes as Active Second-Order NLO Chromophores and Building Blocks for SHG Polymeric Films. J. Organomet. Chem. 2014, 751, 568−572. (18) Angelis, F. De; Belpassi, L.; Fantacci, S. Spectroscopic Properties of Cyclometallated Iridium Complexes by TDDFT. J. Mol. Struct.: THEOCHEM 2009, 914 (1−3), 74−86. (19) Sun, H.; Liu, S.; Lin, W.; Zhang, K. Y.; Lv, W.; Huang, X.; Huo, F.; Yang, H.; Jenkins, G.; Zhao, Q.; Huang, W. Smart Responsive Phosphorescent Materials for Data Recording and Security Protection. Nat. Commun. 2014, 5, 3601. (20) Latouche, C.; Lanoe, P.-H.; Williams, J. A. G.; Guerchais, V.; Boucekkine, A.; Fillaut, J.-L. Switching of Excited States in Cyclometalated Platinum Complexes Incorporating Pyridyl-Acetylide Ligands (Pt–C [Triple Bond, Length as M-Dash] C–Py): A Combined Experimental and Theoretical Study. New J. Chem. 2011, 35 (10), 2196−2202. (21) Savel, P.; Latouche, C.; Roisnel, T.; Akdas-Kilig, H.; Boucekkine, A.; Fillaut, J.-L. Cyclometalated Platinum (II) with Ethynyl-Linked Azobenzene Ligands: An Original Switching Mode. Dalt. Trans. 2013, 42 (48), 16773−16783. (22) Colombo, A.; Dragonetti, C.; Marinotto, D.; Righetto, S.; Roberto, D.; Tavazzi, S.; Escadeillas, M.; Guerchais, V.; Le Bozec, H.; Boucekkine, A.; et al. Cyclometalated 4-Styryl-2-Phenylpyridine Platinum (II) Acetylacetonate Complexes as Second-Order NLO Building Blocks for SHG Active Polymeric Films. Organometallics 2013, 32 (14), 3890−3894. (23) Barbieri, A.; Accorsi, G.; Armaroli, N. Luminescent Complexes beyond the Platinum Group: The d10 Avenue. Chem. Commun. 2008, No. No. 19, 2185−2193. (24) Boixel, J.; Guerchais, V.; Le Bozec, H.; Jacquemin, D.; Amar, A.; Boucekkine, A.; Colombo, A.; Dragonetti, C.; Marinotto, D.; Roberto, D.; Righetto, S.; De Angelis, R. Second-Order NLO Switches from Molecules to Polymer Films Based on Photochromic Cyclometalated Platinum(II) Complexes. J. Am. Chem. Soc. 2014, 136 (14), 5367− 5375. (25) Fillaut, J.; Akdas-Kilig, H.; Dean, E.; Latouche, C.; Boucekkine, A. Switching of Reverse Charge Transfers for a Rational Design of an OFF-ON Phosphorescent Chemodosimeter of Cyanide Anions. Inorg. Chem. 2013, 52 (9), 4890−4897. (26) Zaarour, M.; Singh, A.; Latouche, C.; Williams, J. a G.; LedouxRak, I.; Zyss, J.; Boucekkine, A.; Le Bozec, H.; Guerchais, V.; Dragonetti, C.; Colombo, A.; Roberto, D.; Valore, A. Linear and Nonlinear Optical Properties of Tris-Cyclometalated Phenylpyridine Ir(III) Complexes Incorporating π-Conjugated Substituents. Inorg. Chem. 2013, 52, 7987−7994. (27) Lepeltier, M.; Le Bozec, H.; Guerchais, V.; Lee, T. K.-M.; Lo, K. K.-W. Tris-Cyclometalated Iridium(III) Styryl Complexes and Their Saturated Analogues: Direct Functionalization of Ir(4-Me-ppy)3 and Hydrogen Transfer Process. Organometallics 2005, 24 (24), 6069− 6072. (28) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Kwong, R.; Tsyba, I.; Bortz, M.; Mui, B.; Bau, R.; Thompson, M. E. Synthesis and Characterization of Phosphorescent Cyclometalated Iridium Complexes. Inorg. Chem. 2001, 40 (7), 1704−1711. (29) Okada, S.; Okinaka, K.; Iwawaki, H.; Furugori, M.; Hashimoto, M.; Mukaide, T.; Kamatani, J.; Igawa, S.; Tsuboyama, A.; Takiguchi, T.; Ueno, K. Substituent Effects of Iridium Complexes for Highly Efficient Red OLEDs. Dalt. Trans. 2005, No. 9, 1583−1590.

(30) Culham, S.; Lanoë, P.-H.; Whittle, V. L.; Durrant, M. C.; Williams, J. A. G.; Kozhevnikov, V. N. Highly Luminescent Dinuclear Platinum(II) Complexes Incorporating Bis-Cyclometallating PyrazineBased Ligands: A Versatile Approach to Efficient Red Phosphors. Inorg. Chem. 2013, 52 (19), 10992−11003. (31) Wu, S.-H.; Burkhardt, S. E.; Yao, J.; Zhong, Y.-W.; Abruña, H. D. Near-Infrared Absorbing and Emitting RuII−PtII Heterodimetallic Complexes of Dpdpz (Dpdpz = 2,3-Di(2-Pyridyl)-5,6-Diphenylpyrazine. Inorg. Chem. 2011, 50 (9), 3959−3969. (32) Vazart, F.; Latouche, C.; Bloino, J.; Barone, V. Vibronic Coupling Investigation to Compute Phosphorescence Spectra of Pt(II) Complexes. Inorg. Chem. 2015, 54 (11), 5588−5595. (33) Rajendra Kumar, G.; Thilagar, P. Tuning the Phosphorescence and Solid State Luminescence of Triarylborane-Functionalized Acetylacetonato Platinum Complexes. Inorg. Chem. 2016, 55 (23), 12220−12229. (34) Barone, V.; Bloino, J.; Biczysko, M.; Santoro, F. Fully Integrated Approach to Compute Vibrationally Resolved Optical Spectra: From Small Molecules to Macrosystems. J. Chem. Theory Comput. 2009, 5 (3), 540−554. (35) Barone, V.; Baiardi, A.; Biczysko, M.; Bloino, J.; Cappelli, C.; Lipparini, F. Implementation and Validation of a Multi-Purpose Virtual Spectrometer for Large Systems in Complex Environments. Phys. Chem. Chem. Phys. 2012, 14 (36), 12404−12422. (36) Latouche, C.; Baiardi, A.; Barone, V. Virtual Eyes Designed for Quantitative Spectroscopy of Inorganic Complexes: Vibronic Signatures in the Phosphorescence Spectra of Terpyridine Derivatives. J. Phys. Chem. B 2015, 119 (24), 7253−7257. (37) Baiardi, A.; Bloino, J.; Barone, V. General Time Dependent Approach to Vibronic Spectroscopy Including Franck−Condon, Herzberg−Teller, and Duschinsky Effects. J. Chem. Theory Comput. 2013, 9 (9), 4097−4115. (38) Licari, D.; Baiardi, A.; Biczysko, M.; Egidi, F.; Latouche, C.; Barone, V. Implementation of a Graphical User Interface for the Virtual Multifrequency Spectrometer: The VMS-Draw Tool. J. Comput. Chem. 2015, 36 (5), 321−334. (39) Baiardi, A.; Bloino, J.; Barone, V. Accurate Simulation of Resonance-Raman Spectra of Flexible Molecules: An Internal Coordinates Approach. J. Chem. Theory Comput. 2015, 11 (7), 3267−3280. (40) Baiardi, A.; Latouche, C.; Bloino, J.; Barone, V. Accurate yet Feasible Computations of Resonance Raman Spectra for Metal Complexes in Solution: [Ru(bpy)3](2+) as a Case Study. Dalton Trans. 2014, 43 (47), 17610−17614. (41) Banerjee, S.; Baiardi, A.; Bloino, J.; Barone, V. Vibronic Effects on Rates of Excitation Energy Transfer and Their Temperature Dependence. J. Chem. Theory Comput. 2016, 12 (5), 2357−2365. (42) Latouche, C.; Skouteris, D.; Palazzetti, F.; Barone, V. TD-DFT Benchmark on Inorganic Pt(II) and Ir(III) Complexes. J. Chem. Theory Comput. 2015, 11 (7), 3281−3289. (43) Latouche, C.; Palazzetti, F.; Skouteris, D.; Barone, V. HighAccuracy Vibrational Computations for Transition Metal Complexes Including Anharmonic Corrections: Ferrocene, Ruthenocene and Osmocene as Test Cases. J. Chem. Theory Comput. 2014, 10 (10), 4565−4573. (44) Belaidi, H.; Belaidi, S.; Katan, C.; Latouche, C.; Boucekkine, A. Vibronic Coupling to Simulate the Phosphorescence Spectra of Ir(III)Based OLED Systems: TD-DFT Results Meet Experimental Data. J. Mol. Model. 2016, 22 (11), 265. (45) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; 1754


Article

Journal of Chemical Theory and Computation Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V; Cioslowski, J.; Fox, D. J. Gaussian09 Revision D.01; Gaussian, Inc.: Wallingford, CT, 2009. (46) Becke, A. D. Density-Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98 (7), 5648. (47) Perdew, J. P. Density-Functional Approximation for the Correlation Energy of the Inhomogeneous Electron Gas. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33 (12), 8822−8824. (48) Perdew, J. P.; Burke, K.; Wang, Y. Generalized Gradient Approximation for the Exchange-Correlation Hole of a Many-Electron System. Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 54 (23), 16533−16539. (49) Dunning, T. H., Jr.; Hay, P. J. Gaussian Basis Sets for Molecular Calculations. In Methods of Electronic Structure Theory SE - 1; Schaefer, H., III, Ed.; Modern Theoretical Chemistry; Springer: US, 1977; Vol. 3, pp 1−27. (50) Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for K to Au Including the Outermost Core Orbitals. J. Chem. Phys. 1985, 82 (1), 299. (51) Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for the Transition Metal Atoms Sc to Hg. J. Chem. Phys. 1985, 82 (1), 270. (52) Wadt, W. R.; Hay, P. J. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for Main Group Elements Na to Bi. J. Chem. Phys. 1985, 82 (1), 284. (53) Cossi, M.; Scalmani, G.; Rega, N.; Barone, V. New Developments in the Polarizable Continuum Model for Quantum Mechanical and Classical Calculations on Molecules in Solution. J. Chem. Phys. 2002, 117 (1), 43. (54) Barone, V.; Cossi, M.; Tomasi, J. A New Definition of Cavities for the Computation of Solvation Free Energies by the Polarizable Continuum Model. J. Chem. Phys. 1997, 107 (8), 3210. (55) Berthier, G. Extension de La Méthode Du Champ Moléculaire Self-Consistent À L’étude Des États À Couches Incomplètes. C. R. Hebd. Seances Acad. Sci. 1954, 238, 91−93. (56) Gourlaouen, C.; Daniel, C. Spin-Orbit Effects in Square-Planar Pt(ii) Complexes with Bidentate and Terdentate Ligands: Theoretical Absorption/emission Spectroscopy. Dalt. Trans. 2014, 43 (47), 17806−17819. (57) Daniel, C. Absorption Spectroscopy, Emissive Properties, and Ultrafast Intersystem Crossing Processes in Transition Metal Complexes: TD-DFT and Spin-Orbit Coupling. In Density-Functional Methods for Excited States; Ferré, N., Filatov, M., Huix-Rotllant, M., Eds.; Springer International Publishing: Cham, Switzerland, 2015; pp 377−413. (58) Harabuchi, Y.; Eng, J.; Gindensperger, E.; Taketsugu, T.; Maeda, S.; Daniel, C. Exploring the Mechanism of Ultrafast Intersystem Crossing in Rhenium(I) Carbonyl Bipyridine Halide Complexes: Key Vibrational Modes and Spin−Vibronic Quantum Dynamics. J. Chem. Theory Comput. 2016, 12 (5), 2335−2345. (59) Brahim, H.; Daniel, C.; Rahmouni, A. Spin−orbit Absorption Spectroscopy of Transition Metal Hydrides: A TD-DFT and MSCASPT2 Study of HM(CO)5 (M = Mn, Re). Int. J. Quantum Chem. 2012, 112 (9), 2085−2097. (60) Barone, V. Anharmonic Vibrational Properties by a Fully Automated Second-Order Perturbative Approach. J. Chem. Phys. 2005, 122 (1), 014108. (61) Biczysko, M.; Panek, P.; Scalmani, G.; Bloino, J.; Barone, V. Harmonic and Anharmonic Vibrational Frequency Calculations with the Double-Hybrid B2PLYP Method. J. Chem. Theory Comput. 2010, 6 (7), 2115−2125. (62) Curutchet, A.; Le Bahers, T. Modeling the Photochromism of SDoped Sodalites Using DFT, TD-DFT, and SAC-CI Methods. Inorg. Chem. 2017, 56 (1), 414−423.

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