Solar RRL - 2023 - Bagemihl - Gatekeeping Effect of Ancillary Ligand On Electron Transfer in Click Chemistry Linked

RESEARCH ARTICLE
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Gatekeeping Effect of Ancillary Ligand on Electron Transfer

in Click Chemistry-Linked Tris-Heteroleptic Ruthenium(II)
Donor–Photosensitizer–Acceptor Triads
Benedikt Bagemihl, Andrea Pannwitz,* and Sven Rau*
charge transfer, and storage of redox

Stable charge-separated states are key features for using light in various types of equivalents on viologen-type molecules
solar cells and a broad range of photocatalytic applications. So far, molecular rendered highly active photocatalytic sys-
systems often suffer from increased charge recombination after initial excitation. tems. Covalent linkage between viologen
electron acceptors and catalytically active
Herein, the scope of molecular model systems for intramolecular electron
metal centers led to an overall improve-
transfer and charge separation by applying copper-catalyzed click chemistry to ment of catalytic activity with respect to
covalently functionalize tris-heteroleptic ruthenium(II) complexes to yield donor– attainable turnover numbers and frequen-
photosensitizer–acceptor triads with 1,4-dihydro-N-benzyl-nicotinamide (BNAH) cies.[21] Within these studies, a metal-based
as donor and N-methyl-4,4´-bipyridinium (MQþ) as acceptor is studied. Two photosensitizer always reacted with a
molecular sacrificial donor, such as
triads with electron-withdrawing or electron-donating ancillary 2,2´-bipyridyl
ethylenediaminetetraacetic acid, and the
ligands are synthesized and their light-induced intramolecular electron transfer viologen unit was either linked to the pho-
and long-lived charge-separated states (τ = 0.8 ms and τ = 1.5 ms) are charac- tosensitizer,[22] the catalytically active metal
terized using steady-state and time-resolved spectroscopy and electrochemistry. center[23] or simply added within a pure
Additionally, it is found that the charge-separated state resides on different parts intermolecular approach.[21] Thus, crucial
of the molecule within these two triads, allowing for selective directionality of insights into electron transfer dynamics
between donor, photosensitizer, and accep-
charge transfer within a molecule.
tor could not be elucidated in detail.
To understand these details, molecular
triads that combine electron-donating and
1. Introduction accepting parts in one molecule[24–26] can be used as models
for the photo-induced transfer of electrons as studied by Meyer
For the implementation of solar energy conversion to produce et al. as well as Sakai et al. for phenothiazine-based triads.[27,28]
alternatives to fossil fuels, it is of fundamental interest to Especially if short distances between donor and acceptor are
control and understand electron transfer on a molecular level. involved, charge recombination is always competing electron
This helps in understanding and improving, e.g., dye- transfer. Molecular triads are ideal systems for long-lived charge
sensitized photocatalysis on surfaces, i.e., dye-sensitized separated states as the photosensitizer induces light-driven elec-
photoelectrochemical cells[1–4] or dye-sensitized solar cells tron transfer and consequently blocks recombination pathways,
(DSSCs),[5–7] in light-driven catalysis,[8,9] energy storage,[10–13] therefore enabling electron transfer beyond initially excited state
and biomimetic photocatalytic systems.[14–18] photochemistry.
Within the context of light-driven hydrogen formation, pio- Copper-catalyzed azide-alkyne cycloaddition (CuACC, “click”
neering work by Kiwi and Grätzel[19] and subsequently, Sakai chemistry) introduced by Meldal and Sharpless[29–31] can be used
and Ozawa[20] did show that the combination of light absorption, to link a wide variety of functional groups. It has evolved into one
of the main techniques in a synthetic chemist’s toolbox, which
recently has been awarded by the Nobel prize in chemistry for
B. Bagemihl, A. Pannwitz, S. Rau
Institute of Inorganic Chemistry I
Sharpless, Meldal, and Bertozzi. On ruthenium(II) complexes,
Ulm University it could be shown that anchorage of organic units[31] and charge
Albert-Einstein-Allee 11, 89081 Ulm, Germany transfer in such triazole architectures[32–34] is possible. Although
E-mail: andrea.pannwitz@uni-ulm.de; sven.rau@uni-ulm.de the charge transfer abilities of the 1,4-substituted 1,2,3-triazole
The ORCID identification number(s) for the author(s) of this article in one example could not compete with fully conjugated
can be found under https://doi.org/10.1002/solr.202201135. linkers,[35,36] its enormous application possibilities still make it
© 2023 The Authors. Solar RRL published by Wiley-VCH GmbH. This is an
a popular and versatile linking strategy.
open access article under the terms of the Creative Commons Attribution- This versatility of click chemistry in combination with the syn-
NonCommercial License, which permits use, distribution and thesis of highly diversifiable tris-heteroleptic complexes[37] allows
reproduction in any medium, provided the original work is properly to build up triads that easily enable screening and exchange of
cited and is not used for commercial purposes. both donors and acceptors via postfunctionalization rather than
DOI: 10.1002/solr.202201135 redesigning or extension of the ligand sphere. Importantly, since
Sol. RRL 2023, 7, 2201135 2201135 (1 of 10) © 2023 The Authors. Solar RRL published by Wiley-VCH GmbH
2367198x, 2023, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/solr.202201135 by Indian Institute of Technology Indore, Wiley Online Library on [13/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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the core of the ruthenium complex stays equal, [Ru(bpy)3]2þ-like of time-resolved emission and transient absorption spectroscopy,
photochemistry remains the same for the family of complexes electrochemistry, and spectro-electrochemistry to study the
obtained via postfunctionalization and therefore gives the possi- photo-induced electron transfer and recombination across the
bility to focus more on the interplay of donor and acceptor. triazole bridge.
In this study, we will use CuACC to link N-benzyl-nicotinamide The variation between the peripheral “ancillary” ligand of the
(BNAþ) and N-methyl-4,4 0 -bipyridinium (monoquat, MQþ) suc- triads fRuMQþBNAH and tBuRuMQþBNAH showed to yield
cessively to a bis-(1,10-phenanthroline)-4,4 0 -substituted 2,2 0 -bipyr- contrary photophysical behavior[53,54] and was therefore consid-
idine ruthenium(II) chromophore and then convert BNAþ on ered to influence the charge transfer in the triads.
complex to dihydro 1,4-dihydro-N-Benzyl-nicotinamide (BNAH)
to form the triads depicted in Figure 1.
BNAH, a mimic of the natural reduction equivalent NADPH, 2. Results and Discussion
has intensively been used as an irreversible one electron donor in 2.1. Synthesis and Characterization
photocatalysis by Ishitani et al.[38–40] However, it is formally a
hydride donor[41,42] and therefore, a potential two-electron/ For the synthesis of these compounds, we refined the strategies
one-proton donor, but these circumstances have only rarely been for synthesizing tris-heteroleptic ruthenium(II) complexes on
used.[43,44] Where BNAH and other hydride donors have been the basis of reported procedures[55–57] and additionally added
implemented intramolecularly by coordination to a ruthenium the possibility of performing click chemistry on the com-
terpyridine complex with a free coordination site[45,46] or were plexes.[31] A rough synthesis overview is sketched in Scheme 1
included into the ligand backbone,[47,48] to the best of our knowl- and 2; a more detailed description can be found in the synthetic
edge, only 1 s sphere linkage of BNAH for photo-electrocatalytic section in the Supporting Information in Chapters 4 and 5.
purposes was achieved so far by Zhao et al.[49]
Very importantly, BNAH in its oxidized form BNAþ can easily
2.1.1. Building the Tris-Heteroleptic Ruthenium Core
be introduced into molecular scaffolds and carried through the
synthetic process. As it is no reducing agent, this prevents the
By starting with the ruthenium carbonyl polymer as performed
formation of unwanted sideproducts. Subsequent reductive by Anderson et al., the first 2,2 0 -bipyridine-based ligand (bpy, i.e.,
activation generates the active donor BNAH.[50] fbpy or tbbpy) was introduced in a simple reflux reaction in
On the electron-accepting side, monoquat is a well- methanol to yield the trans-dichlorido ruthenium(II) carbonyl
investigated electron-accepting and protonation-sensitive complexes as shown by Haukka et al. by X-ray crystallographic
derivative of methyl viologen (MV2þ) that has been used in sev- characterization[58] (step not shown in Scheme 1). Instead of
eral electron transfer studies due to its prominent MV2þ-like using triflic acid or silver reagents to remove the carbonyl ligands
absorption in the protonated and reduced state.[51,52] for the coordination of the second ligand, we applied milder
The triads [Ru(tbbpy)(MQþ5-phen)(BNAH5-phen)](PF6)3 for photo-substitution conditions of Vos et al.[56] using a custom-
BNAH (tBuRuMQþBNAH with tbbpy = 4,4 0 -di tert-butyl-2,2 0 - built LED irradiation setup (365 nm peak emission wavelength)
bipyridin) and [Ru(fbpy)(MQþ5-phen)(BNAH5-phen)](PF6)3 to irradiate the reaction in acetonitrile solution over 16 h
(fRuMQþBNAH with fbpy = 4,4 0 -ditrifluoromethyl-2,2 0 -bipyri- (Scheme 1a). Without further purification, the resulting photo-
dine) are depicted in Figure 1 and are investigated by means substitution product, a mix of [Ru(bpy)Cl2(CH3CN)2] and
[Ru(bpy)(CH3CN)3Cl]Cl (with bpy = fbpy, tbbpy) as shown
by Deronzier et al.,[59] was reacted with in 5-position
TIPS-functionalized 1,10-phenanthroline (with TIPS =
(triisopropyl)silyl group, TIPS5-phen)[60] in acetone (Scheme 1a).
The resulting neutral bis-chlorido ruthenium(II) complex
(tBuRuCl2 or fRuCl2, respectively) was then isolated and
reacted with the third ligand 5-ethinyl-1,10-phenanthroline
(alkyne5-phen) in ethanol–water mixtures, and precipitation using
hexafluorophosphate gives the triad precursors fRu and tBuRu in
medium-high yields (Scheme 1b).
Due to the two nonsymmetric phenanthroline ligands, the
NMR characterization of the two triad precursors was challeng-
ing and performed based on selected signals in comparison with
the previous intermediate and starting material (for a detailed
discussion, see Chapter 4.6 in the Supporting Information).
2.1.2. Triad Formation via Click Chemistry
From both donor BNAþ and acceptor MQþ, azide forms were syn-
Figure 1. Scheme and detailed chemical structure of the donor–photosen- thesized (for synthetic procedure, see Chapter 3 in the Supporting
sitizer–acceptor triads investigated in this work: fRuMQþBNAH and Information), namely BNAþ-N3 and MQþ-N3, and suitable crys-
tBu
RuMQþBNAH. PS = photosensitizer. tals of the two azides could be grown by the layering technique.
Scheme 1. Synthesis overview for the synthesis of the tris-heteroleptic core of the triads. The first yield refers to the CF3-substituted derivative, and the
second one to the tBu-derivative. For clarity reasons, the synthesis sequence is only shown by the example of one regioisomer; a = 1) acetonitrile, 365 nm
LED, 2) acetone, TIPS5-phen; b = 1) ethanol/ water (3:1), alkyne5-phen, 2) NH4PF6/water.
Scheme 2. Synthesis overview for the postfunctionalization of the triads by click chemistry. The first yield refers to the CF3-substituted derivative, the
second one to the tBu-derivative. For clarity reasons, the synthesis sequence is only shown by the example of one regioisomer; a = 1) MQþ-N3,
CuSO4, NaAsc, acetone/ water, 2) KF, methanol, 3) NH4PF6/ water; b = 1) BNAþ-N3, CuSO4, NaAsc, acetone/ water, 2) NH4PF6/water. For the
crystal structures of the azides shown on the left side of the scheme, hydrogen atoms are omitted for clarity, and thermal ellipsoids are shown at
50% probability level.
The single crystal structures are depicted in Scheme 2 and can be the changes to the formation of BNAH at 365 nm from
found in the CCDC database under the identifiers 2 225 422 BNAþ. Consequently, this BNAþ reveals as a negative contribu-
and 2 225 423. In the following, they were reacted in two conse- tion in Figure 2b,c. To speed up the reduction process but not
cutive copper-catalyzed azide-alkyne click reactions with the being harmful with the sensitive product, the catalysis was
tris-heteroleptic precursors fRu and tBuRu, for which the synthesis performed at 50 °C in a water bath, where satisfying conversion
is described in the Supporting Information in Chapter 4. was obtained based on the extinction coefficient of BNAH.
For the first click reaction, the free alkyne group was function- At room temperature under equal conditions, the reaction was
alized with the MQþ acceptor, followed by fluoride-induced substantially slower (see Figure S40, Supporting Information)
cleavage of the TIPS-group (Scheme 2a) and subsequent clicking in the triads. The connected (non-difference) UV–vis spectra
of the BNAþ-N3 (Scheme 2b) to yield the respective oxidized tri- and steady-state emission spectra of this process can be found
ads fRuMQþBNAþ and tBuRuMQþBNAþ. in the Figure S39, Supporting Information. Therein, a clear trend
The click reactions were performed under modified reaction in quenching of the steady state emission upon activation of
conditions compared to previously reported ones.[31] However, tBu
RuMQþBNAþ to tBuRuMQþBNAH becomes apparent that
since some of our complexes showed only poor solubility in is not present in fRuMQþBNAþ/ fRuMQþBNAH. This points
dichloromethane, we changed the solvent to an acetone–water out the importance of the exact quenching mechanism of the
mixture and performed the reaction in an ultrasonication bath light-induced electron transfer.
as recently reported,[61] which kept click-typical room tempera-
ture but reduced the reaction time to only 1 h and significantly
2.2. Charge Separation in the Triads
improved yields of the click reaction compared to previous
attempts without ultrasonication.
The mechanism of light-induced charge transfer was elucidated
The purity and identity of the complexes were proven by 1H,
19 using transient absorption and time-resolved emission spectros-
F (for trifluoromethyl-substituted compounds), and 13C-NMR
copy, as depicted in Figure 3 for the activated fRuMQþBNAH
spectroscopy, as well as MALDI mass spectrometry.
and in Figure 4 for the activated triad tBuRuMQþBNAH. To
exclude any interference by the sodium formate and the
2.1.3. Reductive Activation of the Triads [(tbbpy)Rh(Cp*)Cl]Cl precatalyst, which were present in solution
from the activation procedure of the donor site, reference meas-
To activate the triad, the BNAþ substituent of fRuMQþBNAþ and urements were performed in the absence of these additives,
tBu
RuMQþBNAþ was reduced to the electron-donating BNAH which altogether showed no sign of influence on the kinetic
substituent. Due to its regio-selectivity, a Rh-catalyzed BNAþ or spectral transient absorption data (see Chapters 12.2–12.4,
reduction[62–65] was preferred for this over a rather unselective Supporting Information). In addition, Stern–Volmer type experi-
uncatalyzed reduction. Extraction of the reduced product from ments with sodium formate and [(tbbpy)RhCp*Cl]Cl as quench-
the catalytic mixture would have entailed the workup of the very ers in dry, de-aerated methanol solution were conducted and can
light-sensitive BNAH-on-ruthenium(II) compound. On a model be found in the supporting information in Chapter 12.5. Therein,
compound, the reduction was successful, but after workup no interaction in the concentration range relevant to the spectro-
(extraction from DCM/water, filtration through Celite and Rh scopic investigations could be detected.
scavenger Quadra Pure TU, Sigma Aldrich, removal of solvent) The emission decay kinetics at the respective emission maxima
under inert atmosphere in an Ar-filled glovebox, reoxidation was of the activated triads show mono-exponential lifetimes of 0.4 and
observed by 1H-NMR. Therefore, an in situ process was pre- 1.7 μs for fRuMQþBNAH and tBuRuMQþBNAH, respectively and
ferred in the following. are assigned to the decay of the 3MLCT excited state. The transient
The precatalyst [(tbbpy)Rh(Cp*)Cl]þ was chosen and com- absorption data for both activated triads exhibit positive excited
bined with the terminal hydride donor sodium formate and state contributions below 400 nm and a ground state bleach
the unactivated fRuMQþBNAþ or tBuRuMQþBNAþ, respectively. between 400 and 500 nm, characteristic for an 3MLCT excited state
Methanol was chosen as a solvent as it dissolved sufficient in ruthenium polypyridyl complexes.[67] The ground state bleach
amounts of sodium formate (20 mM) as well as the triads. in both activated triads decays with the same lifetime as the respec-
The catalytic process of this reduction works as follows:[50] tive 3MLCT emission, supporting the assignment of a 3MLCT
sodium formate activates the catalytic Rh-site and liberates carbon decay for this feature (cf. Figure 3a and 4a).
dioxide by β-hydride elimination to form the rhodium hydride com- Besides the decay of the 3MLCT state, for each activated triad,
plex. The hydride can then reduce the coordinated BNAþ to the two long-lived photoproducts are observed. The final photoprod-
respective BNAH (see Figure 2 and catalytic cycle sketched in ucts show distinct spectral features (see Figure 3c and 4d) tem-
Scheme S4, Supporting Information). The conversion of BNAþ porally well separated and decay with lifetimes of 1.5 and 0.8 ms,
to BNAH can be monitored by UV–vis spectroscopy. Since changes for fRuMQþBNAH and tBuRuMQþBNAH respectively (see
in absorbance are generally small due to the small extinction coef- Table 1). It is noteworthy that the ms long-lived photoproducts
ficient of BNAH at 365 nm compared to the ruthenium complex,[66] for the two triads are different from each other, although the
conversion is best depicted by difference spectra taking the 20 mM same charge separated state, Dþ•-Ru–A•, is expected due to
sodium formate in methanol solution as background. the same substitution introduced by click chemistry, irrespective
By comparing the difference spectra, shown in Figure 2b,c for of the peripheral bpy ligand.
the reduction of tBuRuMQþBNAþ and fRuMQþBNAþ, respec- For tBuRuMQþBNAH, the long-lived species in methanol sol-
tively, to the spectrum of free BNAH, one can clearly assign vent with NaHCO2 from the previous catalytic activation shows
Figure 2. Reductive activation of the triads. a) Scheme of Rh-catalytic reduction of the triads. b) Difference spectra of the Rh-catalytic charging of 25 μM of
the triad tBuRuMQþBNAþ (solid curves), with scaled positive green infill = BNAH and scaled negative blue infill = BNAþBr. c) Difference spectra of the
Rh-catalytic charging of 25 μM of the triad fRuMQþBNAþ (solid curves). (b,c) with positive filled curves (green/yellow) = BNAH and negative filled curves
(blue/red) = BNAþBr. The filled curves are scaled to the highest respective absorbance. The insets in (b,c) show the catalytic conversion calculated on
the basis of the extinction coefficient of BNAH.
Figure 3. Transient absorption and time resolved emission spectroscopy of the triads. a,b) Kinetic decays of the excited states of 25 μM tBuRuMQþBNAH
in methanol with 20 mM NaHCO2 at 20 °C, c) corresponding spectral traces, and d): photoproduct comparison in the presence and absence of NaHCO2
and Rh-catalyst. i) is 20 μs after initial excitation, ii) 12 μs after excitation, filled curves correspond to reference compound reduced by spectroelectro-
chemistry in acetonitrile (blue = BnzMQ•, green = BnzMQHþ•) and are normalized to the respective photoproduct spectra.
absorbance at 370 nm and a broad absorbance between 450 and analysis using a consecutive (A ! B ! C) model, a lifetime
650 nm, as seen in Figure 3d in trace (i). By looking at the kinetic of 74 μs for this process can be assigned besides the lifetime
traces at 370 and 390 nm (see Figure 3b), it becomes apparent of the final photoproduct of 0.8 ms.
that the intensity at 370 nm increases weakly over time, while Spectroelectrochemistry of the acceptor’s reference molecule
at 390 nm a weak decrease of the signal is visible. From this, BnzMQþ under nonprotic conditions in acetonitrile and in the
it can be followed that two opposed processes must lead to this presence of protons (by the addition of trifluoroacetic acid) is
change in intensity, which are connected. By global lifetime shown in Figure 3d as filled curves and is very similar to
Figure 4. Transient absorption and time resolved emission spectroscopy of the triads. a,b) Kinetic decays of the excited states of transient absorption of
50 μM fRuMQþBNAH in methanol with 20 mM sodium formate at 20 °C. c) Corresponding spectral traces. d) Photoproduct comparison with the absor-
bance of the reduced reference compound [Ru(fbpy)(phen)2](PF6)2 obtained from spectro-electrochemistry in acetonitrile (orange-filled curve) and
reverse steady-state absorption of BNAH in methanol (yellow filled curve). All reference spectra are normalized to the respective photoproduct spectra.
Table 1. Summary of lifetime data gained from transient absorption and time-resolved emission. Lifetimes were obtained by global fits to the kinetic data
of the wavelengths of interest using the consecutive model in the kimopack python package.[80]
Species Global fit from ΔOD data Emission lifetime

tBu þ
RuMQ BNAH (in methanol/NaHCO2) 1.5 μs, 74 μs, 0.8 ms at 605 nm: 1.5 μs
RuMQþBNAH (in methanol/NaHCO2)
f
0.36 μs, 77 μs, 1.5 ms at 660 nm: 0.36 μs
tBu
RuMQþBNAþ (in methanol/NaHCO2) 1.38 μs, 8.21 μs, inf. at 605 nm: 1.8 μs
tBu þ þ
RuMQ BNA (in methanol) 1.38 μs, 8.21 μs, inf. at 605 nm: 1.5 μs
tBu
RuMQþBNAþ (in methanol-d4) 1.96 μs, 4.88 μs, inf. at 605 nm: 2.0 μs
previously found spectra for the reduced MQþ.[24] By comparing seems to consist predominantly of the protonated and reduced
the absorption spectra, the two long-lived photoproducts can be MQþ-acceptor. This observation indicates that a charge separa-
assigned to the intramolecularly reduced and protonated tion with long-lived radical species is also generated in the
MQþacceptor with absorption at 390 nm, which then decays into absence of an additional intramolecular donor, making the triad
the reduced, nonprotonated MQþacceptor with a lifetime act as a dyad with an oxidized Ru-center and reduced MQþ moi-
of 74 μs. This product then exhibits a 0.8 ms lifetime and is ety. It also implies that the metal center with the electron-donat-
the final photoproduct visible in Figure 3d, trace (i) featuring ing tbbpy ligand participates in the long-lived radical species.
an absorption maximum at 540 nm. According to thermodynamic considerations, however, the pro-
The oxidized donor would be anticipated to show a bleach at tonated photoproduct is created in a more exergonic process (see
365 nm; however, this was not observed. Figure 5b and electrochemistry in Supporting Information in
Furthermore, photoexcitation of the nonactivated triad Chapter 11), while the nonprotonated photoproduct formation
tBu
RuMQþBNAþ in pure methanol (shown after 12 μs in is almost isoenergetic. This supports that the initial charge sepa-
Figure 3d trace (ii)) leads to a long-lived photoproduct which ration in methanol as solvent is coupled to a proton transfer from
Figure 5. Energetic profile for photoinitiated charge transfer in the triads. a) fRuMQþBNAH and b) tBuRuMQþBNAH. The highlighted parts in the
molecules represent electron density (orange/blue) or holes (red/green). A full discussion of the energy level scheme can be found in the
Supporting Information (Chapter 11).
the solvent molecules to the acceptor, probably due to hydrogen reference complexes can be found in the Supporting
bonding interactions prior to charge transfer. Hydrogen bonding Information in Chapter and under the identifiers 2 226 950
between methanol and the MQþacceptor was observed in the and 2 231 870 in the CCDC database). This reference complex
ground state using 1H-NMR, which indicated a shift of the consists of a ruthenium(II) polypyridyl core with two phenan-
CH-protons in alpha position to the hydrogen bond accepting throline ligands and one fbpy ligand and shows good agreement
nitrogens of the monoquat unit at high methanol concentrations in electrochemical and steady–state UV–vis data with
(see Figure S42, Supporting Information). f
RuMQþBNAþ (see Figure S49 and S50, Supporting
Since the pKa values of formic acid (3.77[68]) and the proton- Information). Thus, it can be considered as nonfunctionalized
ated MQþ (1.96, determined by UV–vis titration, see Chapter 9.1, reference complex for the triad.
Supporting Information) differ by only two units, hydrogen Upon reduction of this reference complex, a prominent
bonding between them and with methanol is expected to take broadband at 500 nm rises (see Figure 3d) which is compatible
place. However, based on the results with the inactivated triad with the band observed in the final long-lived photoproduct of
tBu
RuMQþBNAþ, it is concluded that the initial charge transfer f
RuMQþBNAH indicating that the photoproduct involves the
is likely to take place via a proton-coupled electron transfer reduced ruthenium center.[70] The bleach around 370 nm is
(PCET) mechanism, starting from hydrogen-bonded MQþ accep- assigned to the oxidation of the intramolecular BNAH electron
tor to the protic-methanol (Equation (1)). In a follow-up step, donor and decays with a smaller lifetime of 77 μs but still contrib-
deprotonation of the reduced acceptor can take place by formate utes to the spectrum shown in Figure 4d. The two lifetimes in the
ions in solution to produce the photoproducts shown in final photoproduct can be distinguished in the kinetic curves at
Figure 3d. For the initial PCET step, using the nonactivated triad 370 and 500 nm (see Figure 4b): for the long-lived photoproducts,
tBu
RuMQþBNAþ in methanol or methanol-d4, an inverse kinetic the feature at 500 nm decays slower than the trace at 370 nm, indi-
isotope effect of 0.6 can be extracted, indicating that protonation cating that the light-induced charge transfer takes place from the
is involved in the electron transfer. Recently, Damrauer et al. cor- BNAH donor to the ruthenium center, before the final long-lived
related this effect in ruthenium(II) aquo complex to a solvent photoproduct is formed with the lifetime of 1.5 ms.
equilibrium prior to photoinitiated charge transfer and suggested Using the nonactivated (oxidized) fRuMQþBNAþ, no long-
an increased Ru(III) character of the MLCT state.[69] This sup- lived photoproduct can be found, and the excited state decays
ports the observation of an oxidative quenching of the excited with a mono-exponential lifetime of 0.36 μs which is the same
triad via PCET mechanism and subsequent deprotonation by as observed by the time-resolved emission (0.4 μs, see Chapter
basic formate in solution. 12.3 in the Supporting Information). Thus, no charge separation
is observed (see transient absorption spectra in Figure S49,
BNAþ Ru2þ MQþ þ HO CH3
(1) Supporting Information).
⇋ BNAþ Ru2þ MQþ ··· HO CH3 These observations lead to the conclusion that the internal accep-
tor MQþ in fRuMQþBNAþ is not involved in the light-induced
Furthermore, by reaction of the BNAH donor in processes of the triad, and the molecule acts as a dyad as well
tBu
RuMQþBNAH with nucleophiles, protons are liberated, which (see schematic representation in Figure 6), leading to an excep-
increases the protic character of the formate buffer and might tionally stable charge-separated state.
drive the mechanism by permanent protonation (Equation (2)) The observation of a long-lived photoproduct in this architec-
ture is therefore very exceptional, because dyads typically recom-
BNAH Ru2þ MQþ þ Hþ ⇋ BNAH Ru2þ MQH2þ (2)
bine faster than their intramolecular charge separation process
Subsequent to this first electron transfer step via the proton- can take place.[24,71] Most likely, this is due to the different ori-
ated species, reductive quenching of the oxidized RuIII by BNAH entations of the 1,2,3-triazole and its connected electron transfer
would in theory provide a large driving force of 0.71 eV capabilities (or incapabilities) and mechanisms, as recently
(see Chapter 11 Supporting Information and Figure 5b). compiled by Dietzek et al.[71] Resultingly, the triazole shows
However, the formation of this product has not been observed diode-like electron transfer capabilities.
spectroscopically. A potential reason for this might be the small Furthermore, side reactions of the oxidized donor to either
overlap between the connected orbitals: The electron situated at form BNA-dimers after abstraction of one proton[38,72] or
the BNAH needs to be transferred to the d-orbital on the ruthe- nucleophilic adducts, as observed for the parent compound
nium complex buried within the core of the ruthenium complex. NADH[73–76] cannot be excluded and would stabilize the other-
A small overlap between these two involved states leads to a small wise unpaired radical photoproducts.
|HAB|2 according to the Marcus–Hush electron transfer parame- Based on thermodynamic considerations, a follow-up electron
ter,[70] thereby reducing the transfer rate to a minimum. transfer to the internal MQþ acceptor should be possible with a
Notably, the final long-lived photoproduct produced from moderate driving force of 0.36 eV (see Supporting Information
f
RuMQþBNAH with a lifetime of 1.5 ms is significantly differ- Chapter 11 and Figure 5a) but cannot be observed spectroscopi-
ent. It shows a bleach at around 370 nm and a positive absorption cally. The same accounts for electron transfer to a protonated
feature at 500 nm (Figure 4d). This species is not compatible with acceptor, which would have an even larger driving force
the reduced MQþ acceptor, as observed in the other triad and of 0.66 eV.
was assigned based on spectroelectrochemical data of the The initial charge transfer via reductive quenching of the
reference compound [Ru(fbpy)(phen)2](PF6)2 (with phen = 1,10- ruthenium core is exergonic and observed in other systems based
phenanthroline, synthesis and crystallographic data for the on ruthenium(II) polypyridyl complexes as a result of the
Figure 6. Structures of the triads fRuMQþBNAH and tBuRuMQþBNAH used in this work.
MLCT-excited state being predominantly localized on the fbpy initial charge separated state. In this study, triazoles inhibit det-
ligands.[54,76,77] rimental charge recombination and therefore enable exception-
Typically, this yields luminescent excited states but not long- ally stable, and long-lived charge separated states.
lived charge separated states.[78] The results presented here might open up new design prin-
The thermodynamic considerations were probed in bimolec- ciples for a multitude of (photo-) chemical systems involving
ular Stern–Volmer-type quenching studies between the refer- chemical linkers in molecules or materials for DSSCs and
ence ruthenium(II) compounds with BNAH and BnzMQþ light-driven catalysis.
(see Figure S56 and S57, Supporting Information). It was
observed that the CF3-reference complex is quenched stronger
by electron donor BNAH than with the electron acceptor, which 4. Experimental Section
is in line with the observations and conclusions regarding the Detailed experimental methods and synthesis procedures can be found
triad. Therefore, we can conclude that the initially excited state in the Supporting Information.
charge transfer is from donor to photosensitizer. The subsequent
charge transfer to the intramolecular MQþacceptor is then a ther-
mal electron transfer, which is either blocked by the triazole or a Supporting Information
strong localization on the CF3-bpy ligand, which might be too far
Supporting Information is available from the Wiley Online Library or from
away from the acceptor side and have very low orbital interaction,
the author.
thereby hindering the subsequent charge transfer. For the
tBu-reference complex, on the other hand, only weak quenching
of the excited state complexes was observed for both the donor Acknowledgements
and the acceptor. It is therefore concluded that the initial charge
transfer in tBuRuMQþBNAH is governed by beneficial orbital Pascal Wintergerst is acknowledged for initial assistance with the click
interactions in the MLCT-excited state within the triad where chemistry conditions. B.B. thankfully acknowledges funding by the
Studienstiftung des Deutschen Volkes by means of a PhD scholarship.
photosensitizer and acceptor are linked covalently,[79] and the
This work is also supported by the Deutsche Forschungsgemeinschaft
electron in the excited state is anticipated to be localized on (DFG, project TRR234 “CataLight” project no. 364549901, projects A1
the electron-poor phen ligands (and not the electron-rich tbbpy). and B8). A.P. gratefully acknowledges the Vector Stiftung for financial sup-
port through project number P2019-0110.
Open Access funding enabled and organized by Projekt DEAL.
3. Conclusion
In summary, the molecular triads presented in this work can be Conflict of Interest
easily prepared via modular click reactions on the precursor com-
plex. The utilization of the BNAþ/BNAH electron donor, which The authors declare no conflict of interest.
can be reductively activated after the construction of the
functional molecular unit, allows for significant improvement
in synthetic accessibility. Depending on the ancillary bpy ligand, Data Availability Statement
the molecules show directionality of light-driven charge transfer, The data that support the findings of this study are available from the
involving either only donor and photosensitizer for the more corresponding author upon reasonable request.
electron-withdrawing CF3-substituted bpy-ligand or only photo-
sensitizer and acceptor for the more electron-rich tert-butyl
substituted bpy, therefore acting as a dyad. The directionality
of the charge transfer is attributed to the gatekeeping effect of Keywords
the ancillary bpy ligand in the 3MLCT state, hydrogen bonding click chemistry, electron transfer, modular synthesis, tris-heteroleptic
events with the electron acceptor, and the 1,2,3-triazole in the ruthenium complexes
Received: December 29, 2022 [27] J. J. Concepcion, R. L. House, J. M. Papanikolas, T. J. Meyer, Proc.
Revised: February 17, 2023 Natl. Acad. Sci. U. S. A. 2012, 109, 15560.
Published online: March 25, 2023 [28] J. A. Treadway, P. Chen, T. J. Rutherford, F. R. Keene, T. J. Meyer,
J. Phys. Chem. A 1997, 101, 6824.
[29] V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew.
[1] M. A. Gross, C. E. Creissen, K. L. Orchard, E. Reisner, Chem. Sci. Chem. Int. Ed. 2002, 41, 2596.
2016, 7, 5537. [30] C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67,
[2] M. D. Brady, L. Troian-Gautier, R. N. Sampaio, T. C. Motley, 3057.
G. J. Meyer, ACS Appl. Mater. Interfaces 2018, 10, 31312. [31] P. Wintergerst, K. Witas, D. Nauroozi, M. Schmid, E. Dikmen,
[3] M. S. Eberhart, D. Wang, R. N. Sampaio, S. L. Marquard, B. Shan, S. Tschierlei, S. Rau, Z. Anorg. Allg. Chem. 2020, 646, 842.
M. K. Brennaman, G. J. Meyer, C. Dares, T. J. Meyer, J. Am. [32] C. Herrero, A. Quaranta, M. Charlot, W. Leibl, B. Vauzeilles,
Chem. Soc. 2017, 139, 16248. A. Aukauloo, Inorg. Chem. 2012, 51, 5985.
[4] M. K. Brennaman, R. J. Dillon, L. Alibabaei, M. K. Gish, C. J. Dares, [33] P. Farràs, A. C. Benniston, Tetrahedron Lett. 2014, 55, 7011.
D. L. Ashford, R. L. House, G. J. Meyer, J. M. Papanikolas, T. J. Meyer, [34] A. Baron, C. Herrero, A. Quaranta, M.-F. Charlot, W. Leibl,
J. Am. Chem. Soc. 2016, 138, 13085. B. Vauzeilles, A. Aukauloo, Chem. Commun. 2011, 47, 11011.
[5] O. Langmar, E. Fazio, P. Schol, G. de la Torre, R. D. Costa, T. Torres, [35] L. Zedler, P. Wintergerst, A. K. Mengele, C. Müller, C. Li, B. Dietzek-
D. M. Guldi, Angew. Chem. Int. Ed. 2019, 58, 4056. Ivanšić, S. Rau, Nat. Commun. 2022, 13, 2538.
[6] B. Pashaei, H. Shahroosvand, M. Graetzel, M. K. Nazeeruddin, Chem. [36] L. Zedler, C. Müller, P. Wintergerst, A. K. Mengele, S. Rau, B. Dietzek-
Rev. 2016, 116, 9485. Ivanšić, Chem. A Eur. J. 2022, 28, e202200490.
[7] H. Tian, J. Oscarsson, E. Gabrielsson, S. K. Eriksson, R. Lindblad, [37] C. S. Burke, T. E. Keyes, RSC Adv. 2016, 6, 40869.
B. Xu, Y. Hao, G. Boschloo, E. M. J. Johansson, J. M. Gardner, [38] Y. Tamaki, T. Morimoto, K. Koike, O. Ishitani, Proc. Natl. Acad. Sci. U.
A. Hagfeldt, H. Rensmo, L. Sun, Sci. Rep. 2014, 4, 4282. S. A. 2012, 109, 15673.
[8] J. Huang, J. Sun, Y. Wu, C. Turro, J. Am. Chem. Soc. 2021, 143, 1610. [39] C. Pac, Y. Miyauchi, O. Ishitani, M. Ihama, M. Yasuda, H. Sakurai,
[9] M. G. Pfeffer, C. Müller, E. T. E. Kastl, A. K. Mengele, B. Bagemihl, J. Org. Chem. 1984, 49, 26.
S. S. Fauth, J. Habermehl, L. Petermann, M. Wächtler, M. Schulz, [40] Y. Kuramochi, O. Ishitani, Front. Chem. 2019, 7, 1.
D. Chartrand, F. Laverdére, P. Seeber, S. Kupfer, S. Gräfe, [41] S. Fukuzumi, Y. Kondo, T. Tanaka, J. Chem. Soc. Perkin Trans. 1984, 2,
G. S. Hanan, J. G. Vos, B. Dietzek-ivanšić, S. Rau, Nat. Chem. 673.
2022, 14, 500. [42] S. Ilic, U. Pandey Kadel, Y. Basdogan, J. A. Keith, K. D. Glusac, J. Am.
[10] M. Schulz, N. Hagmeyer, F. Wehmeyer, G. Lowe, M. Rosenkranz, Chem. Soc. 2018, 140, 4569.
B. Seidler, A. Popov, C. Streb, J. G. Vos, B. Dietzek, J. Am. Chem. [43] S. Fukuzumi, T. Suenobu, M. Patz, T. Hirasaka, S. Itoh, M. Fujitsuka,
Soc. 2020, 142, 15722. O. Ito, J. Am. Chem. Soc. 1998, 120, 8060.
[11] S. Amthor, S. Knoll, M. Heiland, L. Zedler, C. Li, D. Nauroozi, [44] M. M. Ali, H. Sato, M. A. Haga, K. Tanaka, A. Yoshimura, T. Ohno,
W. Tobaschus, A. K. Mengele, M. Anjass, U. S. Schubert, Inorg. Chem. 1998, 37, 6176.
B. Dietzek-Ivanšić, S. Rau, C. Streb, Nat. Chem. 2022, 14, 321. [45] Y. Matsubara, K. Koga, A. Kobayashi, H. Konno, K. Sakamoto,
[12] R. Konduri, H. Ye, F. M. MacDonnell, S. Serroni, S. Campagna, T. Morimoto, O. Ishitani, J. Am. Chem. Soc. 2010, 132, 10547.
K. Rajeshwar, Angew. Chem. Int. Ed. 2002, 41, 3185. [46] A. Kobayashi, H. Konno, K. Sakamoto, A. Sekine, Y. Ohashi, M. Iida,
[13] V. W. Hei Lau, D. Klose, H. Kasap, F. Podjaski, M. C. Pignié, E. Reisner, O. Ishitani, Chem. - A Eur. J. 2005, 11, 4219.
G. Jeschke, B. V. Lotsch, Angew. Chem. Int. Ed. 2017, 56, 510. [47] D. E. Polyansky, D. Cabelli, J. T. Muckerman, T. Fukushima,
[14] P. Buday, C. Kasahara, E. Hofmeister, D. Kowalczyk, M. K. Farh, K. Tanaka, E. Fujita, Inorg. Chem. 2008, 47, 3958.
S. Riediger, M. Schulz, M. Wächtler, S. Furukawa, M. Saito, [48] J. T. Muckerman, P. Achord, C. Creutz, D. E. Polyansky, E. Fujita, Proc.
D. Ziegenbalg, S. Gräfe, P. Bäuerle, S. Kupfer, B. Dietzek-Ivanšić, Natl. Acad. Sci. U. S. A. 2012, 109, 15657.
W. Weigand, Angew. Chem. Int. Ed. 2022, 61, e202202079. [49] J. Liu, C. Guo, X. Hu, G. Zhao, Green Chem. 2019, 21, 339.
[15] G. Lin, Y. Zhang, Y. Hua, C. Zhang, C. Jia, D. Ju, C. Yu, P. Li, J. Liu, [50] A. K. Mengele, S. Rau, Inorganics 2017, 5, 35.
Angew. Chem. Int. Ed. 2022, 61, e202206283. [51] A. Pannwitz, O. S. Wenger, Phys. Chem. Chem. Phys. 2016, 18,
[16] N. H. Tran, D. Nguyen, S. Dwaraknath, S. Mahadevan, G. Chavez, 11374.
A. Nguyen, T. Dao, S. Mullen, T. A. Nguyen, L. E. Cheruzel, J. Am. [52] H. Choi, K. Baek, S. T. Toenjes, J. L. Gustafson, D. K. Smith, J. Am.
Chem. Soc. 2013, 135, 14484. Chem. Soc. 2020, 142, 17271.
[17] J. Wen, X. Yang, Z. Sun, J. Yang, P. Han, Q. Liu, H. Dong, M. Gu, [53] M. D. Turlington, L. Troian-Gautier, R. N. Sampaio, E. E. Beauvilliers,
L. Huang, H. Wang, Green Chem. 2020, 22, 230. G. J. Meyer, Inorg. Chem. 2018, 57, 5624.
[18] D. M. Klein, L. Passerini, M. Huber, S. Bonnet, ChemCatChem 2022, [54] R. M. O’Donnell, R. N. Sampaio, G. Li, P. G. Johansson, C. L. Ward,
14, e202200484. G. J. Meyer, J. Am. Chem. Soc. 2016, 138, 3891.
[19] J. Kiwi, M. Grätzel, Nature 1979, 281, 657. [55] K. Monczak, K. Peuntinger, D. Sorsche, F. W. Heinemann,
[20] K. Sakai, H. Ozawa, Coord. Chem. Rev. 2007, 251, 2753. D. M. Guldi, S. Rau, Chem. - A Eur. J. 2014, 20, 15426.
[21] K. Yamauchi, S. Masaoka, K. Sakai, JACS 2009, 131, 8404. [56] D. Mulhern, S. Brooker, H. Görls, S. Rau, J. G. Vos, Dalton Trans.
[22] K. Yamamoto, A. Call, K. Sakai, Chem. A Eur. J. 2018, 24, 16620. 2006, 51, https://pubs.rsc.org/en/content/articlelanding/2006/dt/
[23] K. Yatsuzuka, K. Yamauchi, K. Sakai, Chem. Commun. 2021, b510751b.
57, 5183. [57] P. A. Anderson, G. B. Deacon, K. H. Haarmann, F. R. Keene,
[24] A. Pannwitz, O. S. Wenger, J. Am. Chem. Soc. 2017, 139, 13308. T. J. Meyer, D. A. Reitsma, B. W. Skelton, G. F. Strouse,
[25] H. Loong, J. Zhou, N. Jiang, Y. Feng, G. Xie, L. Liu, Z. Xie, J. Phys. N. C. Thomas, Inorg. Chem. 1995, 34, 6145.
Chem. B 2022, 126, 2441. [58] T. J. J. Kinnunen, M. Haukka, M. Nousiainen, A. Patrikka,
[26] M. Sandroni, A. Maufroy, M. Rebarz, Y. Pellegrin, E. Blart, T. A. Pakkanen, J. Chem. Soc. Dalton Trans. 2001, 2649.
C. Ruckebusch, O. Poizat, M. Sliwa, F. Odobel, J. Phys. Chem. C [59] M.-N. Collomb-Dunand-Sauthier, A. Deronzier, R. Ziessel,
2014, 118, 28388. J. Organomet. Chem. 1993, 444, 191.
[60] Y. Sun, Z. Chen, E. Puodziukynaite, D. M. Jenkins, J. R. Reynolds, [71] C. Müller, S. Bold, M. Chavarot-Kerlidou, B. Dietzek-Ivanšić, Coord.
K. S. Schanze, Macromolecules 2012, 45, 2632. Chem. Rev. 2022, 472, 214764.
[61] B. Sreedhar, P. S. Reddy, Synth. Commun. 2007, 37, 805. [72] Y. Ohnishi, M. Kitami, Bull. Chem. Soc. Jpn. 1979, 52, 2674.
[62] J. Lutz, F. Hollmann, T. V. Ho, A. Schnyder, R. H. Fish, A. Schmid, [73] C. S. Y. Kim, S. Chaykin, Biochemistry 1968, 7, 2339.
J. Organomet. Chem. 2004, 689, 4783. [74] U. Eisner, J. Kuthan, Chem. Rev. 1972, 72, 1.
[63] C. L. Pitman, O. N. L. Finster, A. J. M. Miller, Chem. Commun. 2016, [75] S. A. Acheson, H. N. Kirkman, R. Wolfenden, Biochemistry 1988 27,
52, 9105. 7371.
[64] H. C. Lo, O. Buriez, J. B. Kerr, R. H. Fish, Angew. Chem. - Int. Ed. 1999, [76] M. Furue, K. Maruyama, T. Oguni, M. Naiki, M. Kamachi, Inorg.
38, 1429. Chem. 1992, 31, 3792.
[65] S. Fukuzumi, Y. M. Lee, W. Nam, J. Inorg. Biochem. 2019, 199, 110777. [77] A. Pannwitz, A. Prescimone, O. S. Wenger, Eur. J. Inorg. Chem. 2017,
[66] A. K. Mengele, S. Kaufhold, C. Streb, S. Rau, Dalt. Trans. 2016, 45, 6612. 2017, 609.
[67] P. Müller, K. Brettel, Photochem. Photobiol. Sci. 2012, 11, 632. [78] A. Vlcek, Coord. Chem. Rev. 1998, 177, 219.
[68] E. A. Braude, F. C. Nachod, J. G. Hoffman, Determination of Organic [79] K. Hu, A. D. Blair, E. J. Piechota, P. A. Schauer, R. N. Sampaio,
Structures by Physical Methods, Academic Press, New York, 1955. F. G. L. Parlane, G. J. Meyer, C. P. Berlinguette, Nat. Chem. 2016,
[69] J. T. Hewitt, J. J. Concepcion, N. H. Damrauer, J. Am. Chem. Soc. 8, 853.
2013, 135, 12500. [80] C. Müller, T. Pascher, A. Eriksson, P. Chabera, J. Uhlig, J. Phys. Chem.
[70] M. Kuss-Petermann, O. S. Wenger, J. Am. Chem. Soc. 2016, 138, 1349. A 2022, 126, 4087.

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RESEARCH ARTICLE

Gatekeeping Effect of Ancillary Ligand on Electron Transfer

charge transfer, and storage of redox

2.1.2. Triad Formation via Click Chemistry

Species Global ﬁt from ΔOD data Emission lifetime

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