Article

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Thermally Tunable Dual Emission of the d8−d8 Dimer

[Pt2(μ‑P2O5(BF2)2)4]4−
Thomas Hofbeck,† Yan Choi Lam,‡ Martin Kalbác,̌ § Stanislav Záliš,§ Antonín Vlček, Jr.,*,§,∥
and Hartmut Yersin*,†
†
Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Universitätstrasse 31, D-93040 Regensburg, Germany
‡
Beckman Institute, California Institute of Technology, Pasadena, California 91125, United States
§
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-182 23 Prague, Czech
Republic
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∥
School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom
*
S Supporting Information
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ABSTRACT: High-resolution fluorescence, phosphorescence, as well as

related excitation spectra, and, in particular, the emission decay behavior
of solid [Bu4N]4[Pt2(μ-P2O5(BF2)2)4], abbreviated Pt(pop-BF2), have
been investigated over a wide temperature range, 1.3−310 K. We focus
on the lowest excited states that result from dσ*pσ (5dz2−6pz)
excitations, i.e., the singlet state S1 (of 1A2u symmetry in D4h) and the
lowest triplet T1, which splits into spin−orbit substates A1u(3A2u) and
Eu(3A2u). After optical excitation, an unusually slow intersystem crossing
(ISC) is observed. As a consequence, the compound shows efficient dual
emission, consisting of blue fluorescence and green phosphorescence
with an overall emission quantum yield of ∼100% over the investigated temperature range. Our investigation sheds light on this
extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in
Pt(pop-BF2) are largely forbidden due to spin-, symmetry-, and Franck−Condon overlap-restrictions and, therefore, the ISC time
is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow,
are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC
processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime
also is temperature-dependent, reflecting the relative population of the triplet T1 substates Eu and A1u. The highly resolved
phosphorescence shows a ∼220 cm−1 red shift below 10 K, attributable to zero-field splitting of 40 cm−1 plus a promoting
vibration of 180 cm−1.

■ INTRODUCTION
Face-to-face d8−d8 complexes of Rh(I), Ir(I) and Pt(II) exhibit
compounds.10−12,18 It is accompanied by an increase in the
Pt−Pt stretching frequency.15,19 Owing to the electron density
remarkable spectroscopic, photophysical, and photochemical reorganization upon excitation and long T1 (3A2u) lifetime,
properties, owing in part to dramatic variations in metal−metal Pt(pop) participates in a rich array of photochemical electron
interactions in their ground and lowest electronic excited and atom transfer reactions, characteristic of d8−d8 sys-
states.1−12 In particular, tetrakis(μ-pyrophosphito)diplatinate- tems.6,8,9,13,20
(II) ([Pt2(μ-P2O5H2)4]4−, abbreviated Pt(pop), has been Replacing the terminal hydrogen atoms of Pt(pop) with BF2
investigated extensively, especially with respect to the proper- groups produces [Pt2(μ-P2O5(BF2)2)4]4−, abbreviated Pt(pop-
ties that are related to the lowest excited singlet S1 and triplet BF2), where BF2 groups covalently link different P2O5 bridges.
T1 states.2,3,6−8,13 These states result from 5dσ* → 6pσ The structure of the perfluoroborated complex is more rigid
excitation6,8,14,15 and, within the D4h point group of the than that of Pt(pop) as is, for example, manifested by larger
Pt2(POP)4 molecular core, lead to a singlet state of A2u Pt−Pt stretching energies than in Pt(pop) (see below), and the
symmetry (1A2u) and a related triplet (3A2u). Pt−Pt unit is better shielded from the environment (Figure 1).1
Because this excitation populates a Pt−Pt bonding orbital, A previous photophysical study in solution revealed that
the Pt−Pt interaction is strengthened, as has been documented Pt(pop-BF2) is a unique case of a dual emitter, exhibiting strong
by time-resolved X-ray diffraction16 and EXAFS,3 which fluorescence as well as phosphorescence, with nearly 100% total
indicate Pt−Pt bond contraction by 0.28−0.31 Å upon photoluminescence quantum yield. Its fluorescence decay
excitation. Such bond shortening upon dσ*pσ excitation is
typical for the whole class of d8−d8 complexes,5,17 including Received: December 7, 2015
M 2 [Pt(CN) 4 ]·nH 2 O (M = metal cation) linear chain Published: February 24, 2016

© 2016 American Chemical Society 2441 DOI: 10.1021/acs.inorgchem.5b02839

Inorg. Chem. 2016, 55, 2441−2449
Inorganic Chemistry Article

standing could enable novel photonic applications25 of these

compounds.

■ RESULTS AND DISCUSSION

Pt(pop-BF2) powder exhibits a dual emission: a blue
fluorescence stemming from the singlet S1 (1A2u) (at ∼400
nm) and green phosphorescence from the triplet T1 (3A2u)
(∼515 nm) at ambient temperature (Figure 2). With

Figure 1. DFT-optimized structure of the lowest-energy C 2h Figure 2. Low-resolution photoluminescence spectra of

conformer of Pt(pop-BF2) in vacuum. The parent point group of [Bu4N]4[Pt2(μ-P2O5(BF2)2)4] (Pt(pop-BF2)) in a microcrystalline
the complex’s core is D4h, which is used throughout this paper, unless powder at selected temperatures in the 1.5−310 K range. λexc = 355
stated otherwise. Color code: Pt (blue), P (orange), O (red), B (pink), nm. Highly resolved low-temperature spectra are shown in Figures 4
and F (violet). and 5

decreasing temperature, the fluorescence and phosphorescence

matches the phosphorescence rise, and phosphorescence quantum yields increase and decrease, respectively, while the
intensity increases with increasing temperature while fluo- total photoluminescence quantum yield stays nearly constant,
rescence intensity decreases.1 The singlet to triplet ISC is much close to unity (Figure 3, Table S1). This behavior is related to
slower than in Pt(pop) (a few ps2,21,22) in both temperature-
independent and thermally activated channels.1 A spin−orbit
(SO)-TDDFT theoretical analysis of both Pt(pop) and Pt(pop-
BF2)14 demonstrated the absence of direct spin−orbit
interaction between S1 and T1 states and revealed relatively
weak spin−orbit interactions of these states with high-lying
ligand to metal−metal charge-transfer (LMMCT) triplet and
singlet states, respectively. The lowest T1 substate A1u was
found to be of a pure triplet character. Both fluorescence and
phosphorescence lifetimes of Pt(pop-BF2) are relatively long
(1.6 ns, ∼8 μs at room temperature, respectively), opening the
way for rare comparisons of properties and reactivities of singlet
and triplet excited states. Among other d8−d8 systems,
relatively long-lived (0.2−1.3 ns) fluorescence was also
observed for several dirhodium complexes with bridging Figure 3. Temperature dependence of the fluorescence ϕfluor and
diisocyanide ligands.17,23,24 However, Pt(pop-BF2) is far the phosphorescence ϕphos quantum yields of Pt(pop-BF2) (powder).
best d8−d8 dual emitter with the longest-lived fluorescence and Relative intensities were obtained from the emission spectra and
highest photoluminescence quantum yields. calibrated by measurements in an integrating sphere at T = 77 and 300
To achieve a deeper photophysical understanding of the dual K, respectively (calibration points are marked by red rhomboids). Data
emission from d8−d8 systems and factors controlling their are collected in Table S1.
singlet-state lifetimes and ISC times, we have investigated the
spectroscopy and excited-state decay kinetics of Pt(pop-BF2) the relatively slow and temperature-dependent ISC from the
over a very broad temperature range (1.3−310 K). We report fluorescent singlet to the lower-lying phosphorescent triplet. In
here highly resolved fluorescence and phosphorescence agreement with previous investigations of Pt(pop)6,15,17,19,21,26
emission and excitation spectra, the zero-field-splitting (ZFS) and experimental1 as well as theoretical studies14 of Pt(pop-
of the lowest triplet state 3A2u into spin−orbit substates, as well BF2), the fluorescence and phosphorescence are assigned to
as temperature-dependent kinetics of fluorescence and emissions from the 1A2u and 3A2u states of predominantly dσ*
phosphorescence decays. Our analysis sheds new light on the → pσ (5dz2 → 6pz) origin. Under the influence of spin−orbit
origin of the very slow ISC rate, as well as on singlet and triplet coupling (SOC), the 1A2u state becomes A2u with ∼96% singlet
excited-state decay pathways and mechanisms, whose under- character and small contributions of high-lying triplets of ligand
2442 DOI: 10.1021/acs.inorgchem.5b02839
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Inorganic Chemistry Article

to metal−metal (LMMCT) character that contain contribu-

tions from pπ → pσ and dπ → pσ excitations (Table S2).14 The
3
A2u state splits into A1u(3A2u) and higher-lying 2-fold
degenerate Eu(3A2u) SO states (the parent state in parentheses),
also known as substates. This notation is valid in the D4h Pt2P8
core symmetry and is used in this paper to characterize the
leading parentage. However, in the actual C2h molecular
symmetry,14 1A2u becomes Au and 3A2u (the lowest triplet)
splits into Au(3A2u), aBu(3A2u), and bBu(3A2u) SO states (where
the aBu and bBu correspond to Eu(3A2u) in D4h).27 In particular,
studies of weak transition processes, such as ISC and vibronic
coupling mechanisms have to take the actual C2h molecular
symmetry into account.
The fluorescence band undergoes a small blue-shift upon
decreasing the temperature. Phosphorescence does not show
any observable changes in the peak wavelength and band shape
from ambient temperature to T = 10 K, while the band
maximum undergoes a ∼300 cm−1 red shift upon decreasing
the temperature further to 1.5 K (Figure 2), which is
attributable to freezing out the emission from the higher
lying triplet substate Eu (see below).
The solid-state photoluminescence behavior at higher
temperatures is very similar to that observed1 in a MeCN
solution over a 273−338 K temperature range, showing that
solid-state photophysical effects such as energy transfer to
neighboring molecules or impurity quenching are of little
importance. It follows, that the observed photoluminescence is
attributable to individual Pt(pop-BF2) molecular units.28 This is
due to a self-trapping phenomenon that has been reported for a
number of Cu(I) complexes29,30 and M2[Pt(CN)4]·nH2O
chains.10,31 For Pt(pop-BF2), we have a similar situation due Figure 4. (a) High-resolution emission (fluorescence) and excitation
to Pt−Pt bond shortening in both 1A2u and 3A2u excited states spectra (normalized) of Pt(pop-BF2) powder at 10 K in the 1A1g ↔
(see the next section). 1
A2u (S0 ↔ S1) energy region; λexc(emission spectrum) = 340 nm,
Blue Fluorescence: High Resolution Emission and λdet(excitation spectrum) = 530 nm (phosphorescence region). (b)
Excitation Spectra. The high-resolution fluorescence spec- Enlarged region near to the electronic 0−0 transition in the high-
trum assigned to emission from the 1A2u excited state (S1) and resolution fluorescence spectrum.
the corresponding excitation spectrum are shown in Figure 4. A
clearly resolved 123 cm−1 vibrational progression in the Both the fluorescence and excitation spectra smear out with
fluorescence spectrum corresponds to the Pt−Pt stretching increasing energy separation from the 0−0 transition,
vibration ν(Pt−Pt) in the ground state, in agreement with the demonstrating that the density of vibrational and/or phonon
nonresonant Raman spectrum that exhibits a prominent ν(Pt− modes increases.
Pt) band at the same frequency, assigned by DFT calculations Green Phosphorescence: Highly Resolved Emission
(Figure S1, Table S3). (For comparison: For BaPt(pop), a and Excitation Spectra. High-resolution phosphorescence
vibrational progression of 112 cm−1 has been observed.32) spectra of Pt(pop-BF2) measured at low temperatures are
Moreover, all individual progression members include a low- shown in Figure 5, together with a corresponding excitation
energy vibrational mode of ∼35 cm−1. The relatively large half- spectrum that matches the “spin-forbidden” 1A1g → 3A2u
width of each member of the progression (20−30 cm−1) absorption band (S0 → T1) that was observed1 in the solution
indicates distinct coupling to (local) phonon modes. The absorption spectrum as a broad unresolved feature. The
Huang−Rhys parameter S was estimated from the observed phosphorescence vibrational progression of 123 cm−1 corre-
vibrational progression (Figure 4) as 5−6 (S = v(Iv/Iv‑1), where sponds to the ground-state ν(Pt−Pt) vibration (Table S3),
Iv/Iv‑1 is the intensity ratio of neighboring vibrational satellites while the progression of 168 cm−1 in the excitation spectrum
and v is the vibrational quantum number).33,34 This value accords with Pt−Pt bond strengthening in the dσ*pσ triplet
indicates a relatively large shift of the equilibrium position of excited state. The Huang−Rhys parameter, as estimated from
the excited-state potential energy surface relative to that of the the T = 10 K emission spectrum (resulting from Eu(3A2u)),
ground state.33,34 amounts to S = 7−8. This indicates a slightly larger distortion
The fluorescence excitation spectrum corresponding to the of the T1 state than of the S1 state with respect to the electronic
1
A1g → 1A2u transition (S0 → S1 band) displays a 160 cm−1 ground state S0. The spectra measured at T = 10 K show a very
progression attributable to ν(Pt−Pt) in the 1A2u excited state. weak 0−0 transition at 20 460 cm−1, as determined from
The 37 cm−1 increase relative to the ground-state value overlapping origins of the excitation and phosphorescence
confirms the Pt−Pt bond strengthening upon dσ*pσ excitation. spectra (Figure 5b); this feature is attributable to the higher-
The excitation peak of lowest energy coincides with the lying Eu spin−orbit substate of 3A2u (denoted Eu(3A2u)), whose
highest-energy emission peak at 26 210 cm−1 (Figure 4), which radiative decay to the ground state becomes slightly allowed
corresponds to the 0−0 energy of the 1A1g ↔ 1A2u transition. through weak mixing with higher-lying 1LMMCT Eu states.14
2443 DOI: 10.1021/acs.inorgchem.5b02839
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Inorganic Chemistry Article

indirectly through spin-vibronic coupling whereby promoting

vibration(s) is (are) simultaneously excited.34−37 It can be
deduced from symmetry considerations in C2h that such
promoting mode(s) should be of bg symmetry.38 Indeed, the
Raman spectrum shows bands at 169 and 194 cm−1 assigned by
DFT to bg vibrational modes (Figure S1, Table S3). For
completeness it is remarked that the shift of 220 cm−1 for the
resolved feature, as observed on cooling, is slightly smaller than
the one of the peak maxima. This behavior is an indication of
an involvement of more than just one promoting mode.
Green Phosphorescence: Decay Dynamics and Zero-
Field Splitting. At all temperatures between 1.3 and 310 K,
the phosphorescence decay of Pt(pop-BF2) follows first-order
kinetics (single-exponential decay). In the 1.3−5 K temperature
range, the decay time is very long and remains largely
unchanged at 8.6 ms. It decreases by 3 orders of magnitude
to about 8 μs at 100 K and then stays nearly constant upon
further temperature increases (Figure 6). The data can be fitted

Figure 5. High-resolution emission (phosphorescence) and excitation

spectra of Pt(pop-BF2) (powder) in the range of the S0 ↔ T1
transition of 1A1g ↔ 3A2u symmetry. λexc(emission) = 300 nm,
λdet(excitation) = 520 nm. (a) Full-range spectra. (b) Enlarged 0−0
transition region. Note: 0−0 − 40 − 180 cm−1 denotes the false
phosphorescence origin of the A1u(3A2u) ↔ A1g(1A1g) transition that is
shifted by 220 cm−1 to lower energy with respect to the Eu(3A2u) ↔
A1g(1A1g) 0−0 transition (at 20460 cm−1), out of which 40 cm−1 is the
3
A2u ZFS and 180 cm−1 is the energy of a promoting vibrational mode
inducing the radiative decay from A1u(3A2u) by a spin-vibronic (ν(sv))
mechanism.

Vibrational progressions in both excitation and emission spectra

occur with weak low-energy vibrational or (local) phonon
satellites of about 30 cm−1. Upon a temperature decrease from
10 to 1.3 K, the resolved phosphorescence feature shifts by
∼220 cm−1 to the red. (The maxima display a shift of ∼300
cm−1.) Since the Eu(3A2u) state is not substantially populated at
1.3 K, the corresponding phosphorescence band can be
assigned to the lower-energy A1u(3A2u) state. It also displays
the 123 cm−1 progression (Figure 5a); each of the observed Figure 6. Temperature dependence of the phosphorescence decay
progression members couples to low-energy phonon modes, time of Pt(pop-BF2) powder (a) and solid solution in frozen MeCN at
leadings to band broadening. A weak origin peak is seen at a concentration of about 2 × 10−5 mol/L (b). The same results are
20 240 cm−1, that is 220 cm−1 lower in energy than the obtained for a 10-fold lower concentration. Fitting of the decay time
Eu(3A2u) → A1g 0−0 transition (Figure 5b). This shift data of (a) to eq 1 provides values of the 3A2u zero-field splitting of
corresponds to the zero-field splitting (ZFS) of 40 cm−1 (see ΔE(ZFS) = 40 cm−1 and the Eu emission decay time of τ(Eu) = 4.5 μs.
below) plus the energy of a promoting vibration of about 180 The value τ(A1u) = 8.6 ms represents the decay time measured at the
plateau. λexc = 355 nm, λdet = 510 nm.
cm−1. The 20 240 cm−1 peak thus represents the false origin of
the A1u(3A2u) → A1g(1A1g) transition, or in the actual C2h
symmetry of the Au[A1u(3A2u)] → Ag[A1g(1A1g)] transition
(with the parentage state symmetries in ascending order in to eq 1, which is based on fast thermal equilibration between
brackets). The corresponding 0−0 transition (expected at two emissive states: a lower nondegenerate A1u(3A2u) and a
20 420 cm−1 = (20460−40) cm−1) is absent from the spectrum, higher doubly degenerate Eu(3A2u) state that are separated by
owing to the pure triplet character of Au[A1u(3A2u)], even in the the energy gap ΔE(ZFS).15,29,34,39,40 At low temperatures,
reduced C2h symmetry (Table S2).14 The observed weak thermal equilibration processes are induced by spin−lattice
emission from the Au[A1u(3A2u)] triplet substate occurs relaxations (SLR).41,42 (Relation 1 remains valid even if the
2444 DOI: 10.1021/acs.inorgchem.5b02839
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Inorganic Chemistry Article

upper Eu(3A2u) state is slightly split in the actual C2h symmetry,

so long as this splitting does not exceed a few cm−1.)

τ (T ) =
1 + 2 exp − ( ΔE(ZFS)
kBT )
1
τ(A1u)
+
2
τ(E u) (
exp −
ΔE(ZFS)
kBT ) (1)
τ(T) represents the measured decay time, kB is the Boltzmann
constant, τ(Eu) and τ(A1u) are the decay times of the
corresponding triplet substates, and ΔE(ZFS) is the 3A2u
zero-field splitting, ΔE(ZFS) = E(Eu) − E(A1u). On the
other hand, no satisfactory fit is obtained assuming non-
degeneracy for both emitting states. Fitting the phosphor-
escence lifetimes to eq 1 yields τ(A1u) = 8.6 ms (corresponding Figure 7. Fluorescence decay of Pt(pop-BF2) powder at different
to the plateau value as displayed in Figure 6a) and τ(Eu) = 4.5 temperatures (inset) and temperature dependence of the decay time
μs, as well as the energy separation between the two states τfluor (black points). λexc = 378 nm (diode laser), λdet = 400 nm. The
ΔE(ZFS) = 40 cm−1. The very long emission decay time (very decay times were obtained without deconvolution of the excitation
strong forbiddenness) and the absence of the related 0−0 pulse profile. The fluorescence decay can be fitted with single-
transition at T ≤ 5 K support the assignment of the low- exponential kinetics over the whole temperature range from 1.3 to 310
temperature emission as stemming from a pure triplet substate, K (inset). The decay time of τfluor = 3.2 ns is nearly temperature-
that is A1u(3A2u). This is further supported by SO-TDDFT independent up to about 100 K and then decreases with increasing
temperature to τfluor = 0.79 ns (310 K). Numerical data in Table S4.
calculations, which show a zero phosphorescence transition
moment in the absence of vibronic coupling.14 In the high-
(Figure 8 and Table S4). With the temperature increasing from
temperature limit (kBT ≫ ΔE(ZFS)), eq 1 simplifies to (in
about 100 to 310 K, the ISC rate increases by a factor of about
analogy to the case described in ref 43):
⎛ 1 2 ⎞
−1
τ(av) = 3⎜ + ⎟
⎝ τ(A1u) τ(E u) ⎠ (2)
Using this equation with lifetimes determined at low temper-
atures (τ(A1u) = 8.6 ms, τ(Eu) = 4.5 μs), an average
phosphorescence decay time τ(av) of about 7 μs is obtained,
closely matching the decay time of τ = 7.9 μs measured at T =
310 K. A very similar decay behavior and red shift upon cooling
from T = 10 to 1.5 K is found for a solid solution of Pt(pop-
BF2) in frozen MeCN (Figure 6b). This similarity shows that
solid-state effects have little impact on the emission properties.
Intersystem Crossing: Rate Constants and Activation
Energies. Whereas ISC in transition metal complexes
frequently occurs within several femtoseconds34,44−51 or less
often on a picosecond34,52−56 time scale, ISC in Pt(pop-BF2) is Figure 8. Temperature dependence of the total fluorescence (ktotal = kr
several orders of magnitude slower.1 The almost 100% total + knr, black), nonradiative (knr = 1/τISC, green), and radiative (kr, red)
emission quantum yield of Pt(pop-BF2) (over the whole decay rate constants of Pt(pop-BF2) powder. Rate constants were
temperature range) indicates that ISC to the phosphorescent determined using relations τfluor = 1/ktot, kr = ϕfluorktot and data from
triplet state is the only nonradiative decay channel of the 1A2u Figures 3 and 7. The fit curve for knr results from eq 3 that refers to a
model of two thermally activated ISC pathways, schematically shown
excited state. Accordingly, we identify the ISC time (τISC) with in the inset. (The kr decrease with temperature increase is tentatively
the nonradiative contribution of the fluorescence decay: τISC−1 attributed to structural variations of the microcrystalline material, also
= knr = (1 − ϕfluor)/τfluor. Using the fluorescence decay time manifested by small shifts of the fluorescence band.) Numerical data in
τfluor and quantum yield ϕfluor values from Figures 7 and 3, Table S4.
respectively, we obtain τISC ≈ 0.9 ns at 310 K, increasing to ∼29
ns below 100 K. These long ISC lifetimes are in striking
contrast with the 660 ps lifetime determined22 (80 K, 2-
MeTHF-propionitrile glass) for Pt(pop), which has a more 30, which indicates that thermally activated ISC processes come
flexible molecular structure. into play (Figure 8).
At low temperatures, the ISC processes that populate the The T-dependent ISC rate can be analyzed using a
lower lying triplet substates of Pt(pop-BF2) are governed by Boltzmann-type model (eq 3), if one assumes fast thermal
spin- and/or symmetry-restrictions. Moreover, the Franck−
equilibration within the low-frequency phonon ladder of the
Condon (FC) factors between the A2u(1A2u) state near its zero-
point vibrational level and the higher-lying vibrational levels of singlet A2u(1A2u) hypersurface in the higher temperature range
the lowest triplet substates A1u(3A2u) and Eu(3A2u) are expected (>100 K) and a T-independent pathway (k0nr) at lower
to be very small, due to similar equilibrium positions.15 Hence, temperatures. Under these assumptions, the T-dependence of
ISC is very slow at low temperature with a nonradiative the nonradiative decay rate constant knr from A2u(1A2u) can be
fluorescence rate constant of k0nr = 3.4 × 107 s−1 (29 ns) fitted to eq 3:29,30,40
2445 DOI: 10.1021/acs.inorgchem.5b02839
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Inorganic Chemistry Article

Scheme 1. Energy Level Diagram and Relaxation

nr
k (T ) =
( ) + k exp(− )
ΔE
k 0nr + k1nr exp − k T1
B
nr
2
ΔE 2
kBT Mechanisms of the Lowest States of Pt(pop-BF2)a
1 + exp(− ) + exp(− )
ΔE1 ΔE 2
kBT kBT (3)

The terms labeled 1 and 2 refer to two different ISC processes

taking place from the zero-point vibrational level of the
A2u(1A2u) state to higher-lying vibrational/phonon levels of the
two triplet substates A1u(3A2u) and Eu(3A2u) (Figure 8, inset). A
good fit (Figure 8) can be obtained only if two activation
energies (ΔE1 and ΔE2) are included. The temperature-
7 −1
independent rate constant knr 0 was determined as 3.4 × 10 s
(29 ns). The two thermally activated pathways become
increasingly important with increasing temperature: knr 1 = 3.9
× 109 s−1 (0.26 ns), ΔE1 = 450 cm−1, and knr 12 −1
2 = 1.3 × 10 s
(0.8 ps), ΔE2 = 1600 cm−1. k1nr and k2nr represent the
isoenergetic ISC rates, while the activation energies ΔE are
given by a number of vibrations and phonons that provide the
required density of overlapping states and sufficiently strong
electronic coupling.
Importantly, spin- and symmetry-restrictions have to be lifted
for these nonradiative relaxation processes, which is possible by
spin-vibronic and/or vibronic mechanisms.35−37,57 The corre-
sponding promoting modes required for these vibronically
induced processes can have different symmetries. In the C2h a
molecular point group, group theoretical considerations show Vibrational Franck-Condon (FC) progressions for the different
that bg, ag, au, and bu can be spin-vibronically or vibronically transitions are also displayed. The electronic A1u → A1g 0-0 transition
active.58 Accordingly, it is very likely that thermal activation is could not be observed due to the pure triplet character of the lowest
substate, but a false origin occurs at 20220 cm−1. This emission
based on the involvement of such promoting modes combined process is induced by a spin-vibronic (sv) mechanism involving a ν(sv)
with low-energy phonon ladders. The activations required to = 180 cm−1 promoting mode. At low temperature (T < 100 K), the
achieve the ISC processes to the two T1 substates are different direct process of intersystem crossing is extremely slow (29 ns), but
and lead to different activation energies ΔE1 and ΔE2.58 becomes thermally activated as the temperature increases. The
From these considerations alone, it is hard to decide whether diagram displays the activation energies that open faster ISC paths
the smaller rate constant knr 1 and the associated activation from the excited singlet state A2u(1A2u) to the two lower lying triplet
energy ΔE1 correspond to the conversion from A2u(1A2u) to substates Eu(3A2u) and A1u(3A2u). Nevertheless, ISC is relatively slow
A1u(3A2u) or Eu(3A2u).59 Tentatively, we attribute the faster knr2
even at ambient temperature. Accordingly, very pronounced dual
process to A2u(1A2u) → Eu(3A2u) because the singlet admixtures emission consisting of blue fluorescence and green phosphorescence is
to Eu(3A2u)14 could increase the electronic coupling. observed, shown as bold vertical arrows. The decay times given in the
diagram refer to temperatures below ca. 80 K.
In conclusion, the proposed model (Scheme 1) is based on
the general understanding14,29,60−62 that direct SOC between
the lowest excited singlet 1A2u and triplet 3A2u state is not corresponding 0−0 transition to the electronic ground state of
effective. Therefore, at low temperature (T < 100 K), the 1
A1g symmetry. The pure triplet character has also been
7 −1
relatively slow ISC time (knr 0 = 3.4 × 10 s , i.e., 29 ns), is confirmed by SO-TDDFT calculations.14 Although the purely
dominated by direct ISC enabled by very small second-order electronic transition is spin-forbidden, emission from the
SO mixing. At higher temperatures, promoting vibrations A1u(3A2u) substate can be induced by a Herzberg−Teller type
combined with phonon-ladders34,63 become active. Vibronic mechanism, in particular, by spin-vibronic process. As a
and/or spin-vibronic coupling pathways are then activated, consequence, the observed vibrational satellite structure is
which have larger electronic coupling and better FC overlap built upon a false origin, which is induced by a promoting mode
between the optically populated A2u(1A2u) state (the S1 state) of 180 cm−1. On the other hand, the higher lying triplet
and the T1 substates. Vibronic and/or spin-vibronic couplings substate Eu(3A2u) shows second-order SOC to higher lying
are essential and required to induce the couplings between the singlets (not to 1A2u), and thus, the transition to the electronic
states of different symmetry and multiplicity. The efficiency of ground state becomes partly allowed. This results in an
thermal ISC activation depends on the final triplet substate. emission decay time that is by a factor of about 2000 shorter
Hence, two different thermally activated ISC rates are observed, than that of the lower triplet substate.
corresponding to ISC conversions to A1u(3A2u) and Eu(3A2u), In this study, we focus particularly on intersystem crossing
respectively.27

■
from the lowest excited singlet state to the two lower lying
triplet substates. The nonradiative fluorescence decay path can
CONCLUDING AND SUMMARIZING REMARKS be identified with the ISC pathways, since the fluorescence
As displayed in Scheme 1, the lowest triplet state 3A2u exhibits a decay matches the rise of the phosphorescence. 1 An
relatively large29 zero-field splitting of ΔE(ZFS) = 40 cm−1 into investigation of the temperature dependence of the ISC rate
the SO substates Eu(3A2u) and A1u(3A2u). The lower lying over a very broad temperature range reveals a deeper insight
substate A1u(3A2u) remains a pure triplet, as is evidenced by its into these mechanisms. The ISC rate is nearly temperature
very long emission decay time of 8.6 ms and the absence of a independent (∼29 ns)−1 up to about 100 K and then increases
2446 DOI: 10.1021/acs.inorgchem.5b02839
Inorg. Chem. 2016, 55, 2441−2449
Inorganic Chemistry Article

with further temperature increase. From these studies, together spectra were corrected for the wavelength dependence of the
with symmetry considerations, it can be concluded that the spectrometer/detector. The decay behavior was recorded using a
nonradiative decay from the 1A2u state to the triplet substates is multichannel scaler card (P7887, Fast ComTec) with time resolution
very slow at low temperatures due to spin- as well as symmetry- down to 250 ps. The fluorescence decay measurements were carried
out with a TCSPC module (PicoHarp 300, PicoQuant). Excitation
restrictions. With temperature increasing above 100 K, two employed the third harmonic (355 nm) of a pulsed Nd:YAG laser
different thermally activated ISC processes to the triplet system (DiNy pQ, IB Laser) or a pulsed diode laser (378 nm,
substates A1u and Eu involving the energies of ΔE1 = 450 PicoBrite, Horiba). A cryostat (Konti IT, CryoVac) was used for
cm−1 and ΔE2 = 1600 cm−1 become relevant (Scheme 1). variable temperature measurements. Quantum yields at ambient
Thus, intersystem crossing is enabled by different kinds of temperature and 77 K were determined using a C9920−02 system
distortions and spin-vibronic couplings.58 These ISC processes (Hamamatsu) with an integrating sphere as a sample chamber. The
are not very fast, since they are induced indirectly by promoting temperature dependence of the quantum yield was determined by
low-frequency vibrations/phonons according to a spin-vibronic recording the emission intensities at different temperatures. These data
and vibronic mechanisms. Moreover, both nonradiative ISC were subsequently calibrated at T = 77 and 300 K using the integrating
sphere.

■
processes require dissipation of a large amount of energy,
equivalent to the S1-T1 gap of 5750 cm−1 (Scheme 1), making
the processes even more inefficient.64 Furthermore, the ASSOCIATED CONTENT
Franck−Condon overlap along the Pt−Pt coordinate will be *
S Supporting Information

rather small due to only slightly different positions of the S1 and The Supporting Information is available free of charge on the
T1 potential energy surfaces (manifested by only slightly ACS Publications website at DOI: 10.1021/acs.inorg-
different Huang−Rhys parameters for the corresponding chem.5b02839.
emissions) and similar vibrational energies of 160 and 168 Numerical values of fluorescence and phosphorescence
cm−1, respectively.65 quantum yields, fluorescence lifetime, and S1 radiative
These factors help explaining why the ISC processes in and nonradiative rate constants at all investigated
Pt(pop-BF2) are much slower than in most other organo- temperatures, calculated spin−orbit transitions and
transition metal complexes, such as Ir(ppy)3 (ppy = phenyl- group theoretical characterizations, experimental and
pyridine) with τ(ISC) < 100 fs,44,45 Pt(thpy)2 (thpy =2- DFT-calculated Raman spectra of Pt(pop-BF2), compu-
thienylpyridine) (50 fs),34 Re(Cl)(CO)3(bpy) (80 fs),47 tational and experimental Raman procedures, and
[Ru(bpy)3]2+ (<30 fs)46 and even Cu(I) complexes with a comparison of selected calculated and experimental
smaller SOC constant showing τ(ISC) of the order of 10 ps.52 bond lengths. (PDF)

■
Given the very similar electronic structures and spin−orbit
coupling, it is surprising that ISC in Pt(pop-BF2) is several
orders of magnitude slower than in analogous Pt(pop) for AUTHOR INFORMATION
which ambient-temperature ISC times in the range 2−30 ps Corresponding Authors
were reported, depending on the solvent, also at T = 80 K, a *E-mail: [email protected].
relatively fast ISC of 660 ps was observed.2,21,22 Assuming the *E-mail: [email protected].
same general excited-state decay mechanism operating for both Notes
complexes (Scheme 1), the much slower ISC in Pt(pop-BF2) is The authors declare no competing financial interest.

■
attributable to its higher structural rigidity and shielding of the
Pt−Pt moiety from intermolecular interactions with counter ACKNOWLEDGMENTS
cations and/or solvent molecules.
The special combination of slow ISC, occurring on a time T.H. and H.Y. acknowledge the financial support of the
scale comparable with radiative fluorescence decay, and the German Ministry of Education and Research (BMBF) and the
large singlet−triplet energy splitting makes Pt(pop-BF2) a very Bavaria California Technology Center (BaCaTeC) for a travel
distinct dual emitter, amenable to fundamental studies of grant. Further financial support was provided by the Ministry of
chemical spin effects. Namely, it is possible to investigate Education of the Czech Republic grants LH13015 and
separately properties and chemistry of the singlet and triplet LD14129, the NSF CCI Solar Fuels Program (CHE-
states of a predominant dσ*pσ character. Besides fundamental 1305124), the Arnold and Mabel Beckman Foundation, and
studies of their spectroscopic and decay properties as presented the COST Action CM1202. M.K. acknowledges the financial
above, the unique properties of Pt(pop-BF2) open the way to support of the MSMT ERC CZ project (LL1301). We thank
applications in new types of optical devices, for example, for Capano Gloria, Ivano Tavernelli, and Majed Chergui (EPFL,
oxygen or temperature sensing25 and dual-emission OLEDs, in Switzerland) as well as Jay. R. Winkler and Harry B. Gray
which all singlet and triplet excitons can be harvested, though in (Caltech) for interesting discussions on intersystem crossing
mechanisms, spectroscopy, and photophysics.

■
two separate states resulting in two-color light emission.

■ EXPERIMENTAL SECTION
Materials. Anhydrous MeCN was used as received from Sigma-
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2448 DOI: 10.1021/acs.inorgchem.5b02839

Inorg. Chem. 2016, 55, 2441−2449
Inorganic Chemistry Article

also thermally promote ISC processes. All these mechanisms can

enlarge the ISC rate.
(59) More correctly written for C2h: Au[A2u(1A2u)] to Au[A1u(3A2u)]
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in an accessible energy range. A very large molecular distortion would
be required to bring suitable pπpσ states energetically close to the
A2u(1A2u) state.

2449 DOI: 10.1021/acs.inorgchem.5b02839

Inorg. Chem. 2016, 55, 2441−2449