Ultrafast Intersystem Crossing vs. Internal Conversion in Î±-diimine

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Spectroscopy and Photochemistry; General Theory

Ultrafast Intersystem Crossing vs. Internal Conversion in #diimine Transition Metal Complexes: Quantum Evidence Maria Fumanal, Etienne Gindensperger, and Chantal Daniel J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.8b02319 • Publication Date (Web): 25 Aug 2018 Downloaded from http://pubs.acs.org on August 25, 2018

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The Journal of Physical Chemistry Letters

Ultrafast

Intersystem

Conversion

in

Crossing

α-diimine

vs.

Internal

Transition

Metal

Complexes: Quantum Evidence Maria Fumanal, Etienne Gindensperger, Chantal Daniel1

Laboratoire

de

Chimie

Quantique,

Institut

de

Chimie

Strasbourg,

UMR7177

CNRS/Université de Strasbourg, 1 Rue Blaise Pascal BP296/R8, F-67008 Strasbourg, France

1

Contact : [email protected]

ACS Paragon Plus Environment

1

The Journal of Physical Chemistry Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT

Whereas 3rd row transition metal carbonyl α-diimine complexes display luminescent properties and possess low-lying triplet metal-to-ligand charge transfer (MLCT) states efficiently accessible by spin-vibronic mechanism, 1st row analogues hold low-lying metalcentered (MC) excited states that could quench these properties. Upon visible irradiation different functions are potentially stimulated, namely luminescence, electron transfer or photo-induced CO release, the branching ratio of which is governed by the energetics, the character and the early time dynamics of the photoactive excited states. Simulations of ultrafast

non-adiabatic

quantum

dynamics,

including

spin-vibronic

effects,

of

[M(imidazole)(CO)3(phenanthroline)]+ (M = Mn, Re), highlight the role of the metal atom. An ultrafast intersystem crossing process, driven by spin-orbit coupling, populates the lowlying triplet states of [Re(imidazole)(CO)3(phen)]+ within the first tens of fs. In contrast, efficient

internal

conversion

between

the

two

lowest

1

MLCT

states

of

[Mn(imidazole)(CO)3(phen)]+ is mediated within 50 fs by vibronic coupling with upper MC and MLCT states.

TOC GRAPHICS

KEYWORDS α-diimine transition metal complexes – photophysics – quantum dynamics – intersystem crossing – internal conversion – ultrafast decay – rhenium - manganese


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Excited-state ultra-fast decays and structural dynamics observed by means of femtosecond time-resolved experiments able to monitor coherent vibrational wavepackets performed on a number of transition metal complexes 1 , 2 , 3 , 4 ,5 , 6 ,7 ,8 ,9 ,10 ,11 , 12 have been interpreted by nonadiabatic dynamics pointing to spin-vibronic mechanisms.13 Most of the time, as illustrated for

Re(I)

carbonyl

α-diimine

luminescent

probes

and

electron

transfer

triggers,14,15,16,17,18,19,20,21 spin-orbit (SOC) and vibronic coupling effects are associated to lead to efficient intersystem crossing.22,23,24,25,26 Analogues Mn(I) complexes, for which no timeresolved experiments are available, are good candidates for the development of new photoinduced CO release materials so-called PhotoCORM used as diagnostic and therapeutic tools. 27 ,28 ,29 ,30 ,31 ,32 ,33 ,34 , 35 The efficiency of PhotoCORM is based on specific properties, namely fluorescence and efficient CO dissociation upon visible irradiation.27 Here we compare the early-time photophysics (< 1 ps) of [Re(imidazole)(CO)3(phen)]+ and [Mn(imidazole)(CO)3(phen)]+ (Figure 1, phen = 1,10-phenanthroline) by means of nonadiabatic quantum dynamics based on the spin-vibronic model within a multi-mode approach using diabatic functions.23 The present study reports original simulations reproducing in real time two fundamental processes, namely ultrafast intersystem crossing (ISC) in the rhenium(I) complex and internal conversion (IC) in the manganese(I) complex. It is shown that the upper excited states, above the absorbing limit (400 nm), are necessary to complete the internal conversion via an electronic-vibration coherent process between electronic states of different characters. These high-lying excited states are never populated as such but do mediate the ultrafast IC.


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Figure 1. Schematic Cs structures of the [M(imidazole)(CO)3(phen)]+ (M= Mn, Re) complexes.

A description of the diabatic Hamiltonian describing the coupled electronic states is provided in the SI. Effective intra- and interstate coupling constants along the normal modes of [Re(imidazole)(CO)3(phen)]+ and [Mn(imidazole)(CO)3(phen)]+ are reported in Tables S2-S5 of SI as well as the SOC values in Tables S6-S7. The quantum dynamics simulations are performed using the multiconfiguration time-dependent Hartree method.36,37,38

The diabatic functions are associated to two sets of low-lying singlet and triplet electronic states, namely set-A that includes the states below the experimental absorption wavelength (400 nm) and set-B that incorporates upper close-lying electronic states of metal-centered (MC) and metal-to-ligand-charge-transfer (MLCT) characters. This leads to at most 9 / 6 singlet and 9 / 8 triplet states, leading to 36 / 30 “spin-orbit” electronic states for the Mn / Re complex, respectively (Table S1 and Figure S1, SI). The model incorporates 15 normal modes associated mainly to the phen and CO vibrations (Figures S2 and S3, SI). The two sets of photoactive excited states of [Re(imidazole)(CO)3(phen)]+ and [Mn(imidazole)(CO)3(phen)]+ included in the spin-vibronic coupling model are represented in Figure 2 by their electronic density characteristics and transition energies. The multiplet components are treated explicitly and spin-orbit coupling (SOC) is included in the coupling


4

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matrix, as well as the intra- and inter-state electron-vibration coupling terms. Details of the calculation of the electronic structure data are reported elsewhere.25,39 (a) [Mn(imidazole)(CO)3(phen)]+ S1 (a1A”) 3.19

S2 (b1A’) 3.43

S3 (c1A’) 3.52

S4 (b1A”) 3.56

S6 (e1A’) 3.65

S7 (c1A”) 3.69

S8 (d1A”) 3.78

S9 (f1A’) 3.86

T1 (a3A’) 2.92

T2 (a3A”) 2.95

T3 (b3A’) 3.09

T4 (b3A”) 3.10

T6 (d3A”) 3.22

T7 (c3A’) 3.23

T8 (e3A”) 3.32

T9 (d3A’) 3.34

S5 (d1A’) 3.59

T5 (c3A”) 3.17

(b) [Re(imidazole)(CO)3(phen)]+ S1 (a1A”) 3.12

S2 (b1A’) 3.40

S3 (c1A’) 3.46

S4 (b1A’) 3.56

S5 (d1A’) 3.76

T1 (a3A”) 2.98

T2 (a3A’) 3.07

T3 (b3A”) 3.24

T4 (b3A’) 3.42

T5 (c3A’) 3.45

T6 (d3A”) 3.56

T7 (c3A’) 3.57

T8 (e3A”) 3.82

S6 (e1A”) 3.83


5


Page 6 of 20

Figure 2. Change of electronic density induced by excitation of the ground state of (a) [Mn(imidazole)(CO)3(phen)]+ and (b) [Re(imidazole)(CO)3(phen)]+ in the singlet and triplet excited states included in the spin-vibronic coupling model. Density loss/gain is shown in red/green.

Set-A

includes 2

singlet (S1,

S2) and 9

triplet (T1-T9) states

of

[Mn(imidazole)(CO)3(phen)]+ and 2 singlet (S1, S2) and 5 triplet (T1-T5) states of [Re(imidazole)(CO)3(phen)]+; Set-B includes 9 singlet (S1-S9) and 9 triplet (T1-T9) states of [Mn(imidazole)(CO)3(phen)]+ and 6 singlet (S1-S6) and 8 triplet (T1-T8) states of [Re(imidazole)(CO)3(phen)]+. (Energies are given in eV)

Results and Discussion The result of two sets of simulations referring to set-A and set-B (Figure 2) is reported in Figure 3 that exhibits the time-evolution of the population of the diabatic electronic states within 500 fs for both complexes.


6

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Figure 3. Time-evolution of the diabatic population of [Mn(imidazole)(CO)3(phen)]+ (right) and [Re(imidazole)(CO)3(phen)]+ (left) including 11 and 7 electronic states, respectively (setA: top) and 18 and 14 electronic states, respectively (set-B: bottom). According to our previous studies performed on the rhenium(I) complexes22-26 and to the experimental findings,15,16 the initially populated absorbing 1MLCT (S2) state decays within a few tens of fs leading to population of T4, T3 and in a lesser extent of T2, driven by SOC within the spin-vibronic picture. The ISC process to the long-lived lowest 3MLCT (T1) state


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Page 8 of 20

is activated within 100 fs by vibronic coupling (Figure 3, left). The lowest singlet state (S1) is not populated: the ISC process occurs readily in the S2 state, in contrast to what Kasha’s rule would predict. These results are established whatever the number of electronic states included in the simulation 7 (set-A) (Figure 3 left top) or 14 (set-B) (Figure 3 left bottom) is. Indeed, when adding the upper 1,3MLCT excited states (S3-S6 and T6-T8) the transfer of population to T1 decreases from 60% to 45% at about 250 fs and the transfer of population to T4 decreases to 20% in the first tens of fs. However, the results are not qualitatively affected: the coupling to higher lying states is weak (Tables S2, S3 SI) and those states barely participate in the ultrafast internal conversion process. This is in contrast to the manganese complex, as we shall discuss now.

When replacing the rhenium atom by a manganese atom, the simulation restricted to 11 electronic states (Set-A, Figure 3 right-top) shows a slow decay of the population of the absorbing 1MLCT (S2) state and minor population of the low-lying excited states. In particular the intersystem crossing process is quenched in this 1st-row transition metal complex because of modest SOC values (Table S7, SI) as compared to the 3rd-row complex (Table S6, SI). Neither SOC, nor vibronic coupling between the two 1MLCT (S1 and S2) states is strong enough for inducing either efficient ISC like in the rhenium analogue or internal conversion. We have shown recently40 that the state correlation diagrams connecting the singlet and triplet excited states of the manganese complex to the products of axial CO and imidazole dissociations are characterized by a number of crossings, nearby the Franck-Condon region, generated by the presence of MLCT and MC states lying up to 0.45 eV above the S2 absorbing state. Even though the dissociation is not studied here since we restrict ourselves to early-time dynamics, this suggests that upper excited states may be important in the context of a vibronic-coupling driven mechanism. These high-lying excited states (Figure 2; set-B) may


8

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activate the early time dynamics of [Mn(imidazole)(CO)3(phen)]+ by inducing vibrationally hot electronic energy decay via transfer of coherences within the excited states manifold.41,42,43,44,45 The results of the simulations depicted in Figure 3 (right-bottom) confirm this hypothesis. Strikingly, when adding the upper MLCT and MC states (Figure 2, set-B) of [Mn(imidazole)(CO)3(phen)]+ to the spin-vibronic model the lowest 1MLCT (S1) state is efficiently populated within 50 fs by exchange of population with S2. The low-lying triplet states remain marginally populated (Figure 3, right-bottom). Interestingly, whereas these upper MC and MLCT excited states are never populated they mediate the exchange of population between S2 and S1 via efficient vibronic coupling. Our hypothesis is that electronic-vibration coherences are preserved within the close-lying excited states during the ultra-fast decay. This could be evidenced experimentally by multidimensional spectroscopy techniques.46,47 The effective vibronic coupling reported in Table 1 (Tables S4, S5 SI) clearly show that S2 and S1 are strongly coupled to higher lying states. In contrast the rhenium complex is characterized by weak vibronic coupling (Tables S2, S3, SI), leading to a minor impact of high-lying states in the context of a spin-orbit coupling driven decay.

The process of internal conversion described here for the manganese complex is incomplete when adding either only the upper MLCT states, or only the upper MC states (Figure 4). An analysis of the dominant normal modes points to the importance of the phen vibrations for activating vibronic coupling with the upper MLCT states whereas carbonyl normal modes control vibronic coupling with the upper MC states (Table 1). This is further illustrated by the results of the quantum dynamics simulations when quenching one set of these modes in Figure 4.


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Table 1. Effective vibronic coupling (in eV) between the singlet S1-S6 and S9 excited states of [Mn(imidazole)(CO)3(phen)]+ associated to the a’ CO modes (460, 646, 691 cm-1), a’ phen modes (471, 749, 1552, 1625, 1661 cm-1) and a” CO modes (95, 475, 637 cm-1). Diagonal terms correspond to intrastate obtained by means of the gradient computed at FC and offdiagonal terms correspond to interstate coupling obtained within the overlap protocol of Ref. 26.

a' (CO) S1 A" S2 A' S3 A' S4 A" S5 A' S6 A' S7 A" S8 A" S9 A'

S1 A" S2 A' S3 A' 0.0320 0.0 0.0415 0.0 0.0250 0.0489 0.0 0.0 0.0365 0.0 0.0223 0.0343 0.0 0.0080 0.0141 0.0201 0.0 0.0 0.0067 0.0 0.0 0.0 0.0438 0.0139

S4 A"

a' (phen) S1 A" S2 A' S3 A' S4 A" S5 A' S6 A' S7 A" S8 A" S9 A'

S1 A" S2 A' S3 A' 0.1957 0.0 0.2111 0.0 0.0421 0.1466 0.0 0.0 0.0616 0.0 0.0643 0.0849 0.0 0.0302 0.0161 0.0060 0.0 0.0 0.0120 0.0 0.0 0.0 0.0502 0.0300

S4 A"

a" (CO) S1 A" S2 A' S3 A' S4 A" S5 A' S6 A' S9 A'

S1 A" S2 A' S3 A' 0.0 0.0137 0.0 0.0 0.0 0.0369 0.0 0.0236 0.0108 0.0 0.0 0.0179 0.0 0.0 0.0253 0.0025 0.0 0.0

S4 A"

0.1252 0.0 0.0 0.0394 0.0195 0.0

0.1410 0.0 0.0 0.0102 0.0083 0.0

S5 A'

0.0966 0.0223 0.0 0.0 0.0261 S5 A'

0.1043 0.0113 0.0 0.0 0.0139

S5 A'

0.0 0.0123 0.0555 0.0203


0.0 0.0 0.0

S6 A'

S9 A'

0.0517 0.0 0.0 0.0239

0.0724

S6 A'

S9 A'

0.2391 0.0 0.0 0.0233

0.1935

S6 A'

S9 A'

0.0 0.0

0.0

10

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Figure 4. Time-evolution of the diabatic population of [Mn(imidazole)(CO)3(phen)]+ including 15 normal modes (top) excluding upper MC states (left) and excluding upper MLCT states (right); switching-off phen normal modes (bottom, left) and switching-off carbonyl normal modes (bottom, right).

When including 15 normal modes but excluding either the MC states (Figure 4 top, left) or the MLCT states (Figure 4 top, right) only 30% and 20 % of the S1 population is recovered within 200 fs, respectively, as compared to the nearly 60% obtained in the full simulation (Figure 3 bottom, (b)). When switching-off either the phen or the carbonyl normal modes the population of S1 remains minor (< 20%) in the first 500 fs (Figure 4 bottom) pointing to the


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key role of the ligand vibrations in the process of internal conversion driven by an electronicvibration coherent process.

This work represents the first quantum evidence of the control of the early time photophysics of coordination compounds by the central metal atom. Both 1st and 3rd-row transition metal complexes exhibit an ultra-fast decay of the absorbing 1MLCT S2 state within 200 fs by means of a spin-vibronic mechanism. Whereas this decay is mainly controlled by SOC between S2 and the low-lying MLCT triplet states in the rhenium (I) complex, it is driven by vibronic coupling between S2 / S1 and the upper singlet MC and MLCT states in the manganese (I) complex. The former case describes a pure S2 → Tn intersystem crossing process where vibronic effects are involved at the latest stage to populate T1. In the later case, in the absence of strong SOC, S2 → S1 internal conversion is not direct but mediated by the upper electronic states of different electronic characters.

The early time photophysics described above prepare the complexes for subsequent functions, namely formation of a charge-separated state from the lowest T1

3

MLCT state of

[Re(imidazole)(CO)3(phen)]+ when linked to the modified pseudomonas aeruginosa azurin protein,19-21 or carbonyl dissociation in the case of [Mn(imidazole)(CO)3(phen)]+ as recently observed for the first luminescent manganese carbonyl-based PhotoCORM recently reported in the literature. 29

ASSOCIATED CONTENT

Supporting Information: Description of the vibronic coupling model including spin-orbit effects and computational details. – Figures of the Kohn-Sham orbitals and important vibrational normal modes (tuning and coupling) of the Mn and Re complexes – Tables of the vibronic and spin-orbit coupling values.


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Acknowledgments This work has been supported by Labex CSC (ANR-10-LABX-0026_CSC) and French/Austrian ANR-15-CE29-0027-01 DeNeTheor. The calculations have been performed at the High Performance Computer Centre (HPC), University of Strasbourg and on the nodes cluster of the Laboratoire de Chimie Quantique (CNRS / University of Strasbourg).

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1418.

CAPTIONS of FIGURES

Figure 1. Schematic Cs structures of the [M(imidazole)(CO)3(phen)]+ (M= Mn, Re) complexes.

Figure 2. Change of electronic density induced by excitation of the ground state of (a) [Mn(imidazole)(CO)3(phen)]+ and (b) [Re(imidazole)(CO)3(phen)]+ in the singlet and triplet excited states included in the spin-vibronic coupling model. Density loss/gain is shown in red/green.

Set-A includes 2

singlet

(S1,

S2) and 9

triplet (T1-T9) states

of

[Mn(imidazole)(CO)3(phen)]+ and 2 singlet (S1, S2) and 5 triplet (T1-T5) states of [Re(imidazole)(CO)3(phen)]+; Set-B includes 9 singlet (S1-S9) and 9 triplet (T1-T9) states of [Mn(imidazole)(CO)3(phen)]+ and 6 singlet (S1-S6) and 8 triplet (T1-T8) states of [Re(imidazole)(CO)3(phen)]+. (Energies are given in eV.)

Figure 3. Time-evolution of the diabatic population of [Mn(imidazole)(CO)3(phen)]+ (right) and [Re(imidazole)(CO)3(phen)]+ (left) including 11 and 7 electronic states, respectively (setA: top) and 18 and 14 electronic states, respectively (set-B: bottom).

Figure 4. Time-evolution of the diabatic population of [Mn(imidazole)(CO)3(phen)]+ including 15 normal modes (top) excluding upper MC states (left) and excluding upper MLCT states (right); switching-off phen normal modes (bottom, left) and switching-off carbonyl normal modes (bottom, right).


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Ultrafast Intersystem Crossing vs. Internal Conversion in Î±-diimine

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