SYNLETT0936-52141437-2096

Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart

2021, 32, 1154–1179
New Tools 1154
Organic Photoredox Catalysis in Synthesis –
Synlett Y. Wu et al. New Tools

Photophysical Properties and Redox Potentials of Photosensitizers

for Organic Photoredox Transformations
Yanyu Wu > 200 photosensitizers summarized
Dooyoung Kim Excited-state properties
ox
*PS S1 T1 E0,0 t *E *Ered
Thomas S. Teets* 0-02741-867
substrate
hn
SET Photoredox catalysis
Department of Chemistry, University of Houston, 3585 Cullen
Blvd., Room 112, Houston, TX 77204-5003, USA product
[email protected]
Published as part of the Cluster PS S0 lmax Eox Ered
Organic Photoredox Catalysis in Synthesis – Honoring Prof. Shunichi
Ground-state properties
Fukuzumi’s 70th Birthday

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Corresponding
Thomas
Department
eMail [email protected]
S. Teets AuthorUniversity of Houston, 3585 Cullen Blvd., Room 112, Houston, TX 77204-5003, USA
of Chemistry,

Received: 22.01.2021 including organic dyes,14–16 inorganic semiconductors,17–19

Accepted: 15.02.2021
transition-metal complexes,7,20 and metal–organic frame-
Published online: 15.02.2021
DOI: 10.1055/a-1390-9065; Art ID: st-2021-p0025-c works,21–23 among others. Molecular PSs are particularly
dominant in the field of photocatalysis on account of the
Abstract Photoredox catalysis has proven to be a powerful tool in maturity of the study of their photochemistry, the control-
synthetic organic chemistry. The rational design of photosensitizers
with improved photocatalytic performance constitutes a major ad-
lability of their structural design, and the potential to per-
vancement in photoredox organic transformations. This review summa- form judicious manipulations of their electronic structure
rizes the fundamental ground-state and excited-state photophysical and redox properties. Most molecular PSs used in photoca-
and electrochemical attributes of molecular photosensitizers, which are talysis are inorganic or organometallic transition-metal co-
important determinants of their photocatalytic reactivity. ordination complexes, with Ir and Ru complexes being
Key words photosensitizers, photoredox catalysis, redox potentials, arguably the most ubiquitous.24–26 Metal-free organic chro-
excited states, photophysics, photochemistry mophores are important alternatives to metal-based PSs,
providing the potential benefits of low cost, easy purifica-
tion, biocompatibility, and low toxicity.15,27
Introduction The catalytic performance of molecular PSs in photore-
dox reactions strongly depends on their photophysical
Photocatalysis, in which light energy is converted into properties and their electrochemical attributes in both the
chemical bonds, was initially studied to facilitate such inor- ground state and excited state. Therefore, it is essential to
ganic transformations as solar water splitting and carbon understand and evaluate these properties to predict how a
dioxide reduction.1–3 Since the pioneering work by the PS will interact with reaction components when designing
groups of MacMillan,4 Yoon,5 Stephenson,6 and many oth- specific photochemical transformations. Review articles on
ers,7 photoredox catalysis has recently garnered much rec- photoredox organic synthesis have mainly focused on
ognition in the context of organic synthesis, permitting a methodology development, with some coverage of molecu-
variety of challenging organic transformations to proceed lar-design principles, electronic structures, excited-state
under mild conditions.8–11 Photochemical reactions are ini- dynamics of the PSs, and mechanistic analyses of various
tiated after light harvesting by photosensitizers. Photosen- types of photocatalytic reaction.7,14,28–31 The objective of
sitizers (PSs) are defined as chemicals that can be promoted this review is to provide a summary of the key photophysi-
to their electronically excited states by absorbing light; the cal data, excited-state energies, and ground-state and excit-
excited molecules then permit the formation of reactive re- ed-state redox potentials of common molecular PSs that
action intermediates by engaging in bimolecular single- have been used in photoredox organic synthesis, so as to
electron transfer (SET) or energy-transfer processes during serve as a practical guide for photoredox catalysis practi-
photocatalysis.12,13 PSs are also referred to as photocatalysts tioners. Partnered with Roth, Romero, and Nicewicz’s cata-
when used in catalytic applications. The continued interest log of ground-state redox potentials published in 2016,32
in new reactivity and improved catalytic performance has which focused primarily on small-molecule substrate mol-
led to the emergence of a number of different types of PSs, ecules, this review should provide researchers with a clear

© 2021. Thieme. All rights reserved. Synlett 2022, 33, 1154–1179

Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany
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Synlett Y. Wu et al. New Tools

picture of the redox thermodynamics when selecting sub- photoluminescence spectrum recorded at a cryogenic
strates and PSs for photoredox transformations. In addition, temperature (normally 77 K) is used to assign E0,0.34,35 Al-
we provide an informative discussion on how to evaluate ternatively, E0,0 has been predicted by computational
and analyze these values in relation to the photocatalytic methods such as density functional theory (DFT) and
reactivity of PSs. Because of the considerable advances time-dependent DFT.36–38
made in the field of photocatalysis, it is not possible to in-
clude every single reported PS. Nevertheless, we have at- Ground-State Redox Potentials
tempted to cover a wide variety of PSs, ranging from organ-
ic molecules to various transition-metal complexes, with a Formal ground-state redox potentials are normally
particular emphasis on those that have been applied in measured by using cyclic voltammetry, a common tech-
photochemical organic reactions. nique for studying the redox processes of molecular spe-
cies.39 Complexes can feature reversible or irreversible cy-

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clic voltammograms, as are shown in Figure 1 and Figure 2,
Photophysical and Electrochemical Properties respectively. The ground-state oxidation potential [Eox or
E(PS+/PS)] and reduction potential [Ered or E(PS/PS–)] are re-
Excited-State Energy lated to the first one-electron oxidation and the first one-
electron reduction events of the PS, respectively, as depict-
Upon absorption of light, usually in the UVA or visible- ed in the modified Latimer diagram (Scheme 1).
light region, a PS is promoted to a singlet excited state and
then normally relaxes rapidly to the lowest-lying vibration-
al level of the lowest singlet excited state (S1). The PS can
also reach its triplet excited state (T1) from the S1 state
through intersystem crossing (ISC). The excited-state ener-
gy (E0,0) is the energy difference between the zeroth vibra-
tional level of the electronic ground state (S0) and the rele-
vant excited state. Rigorously speaking, E0,0 refers only to
singlet states, but it is often also used in conjunction with
triplet states. E0,0 can also be abbreviated as ES1 or ET1, corre-
sponding to the lowest-lying singlet and triplet excited
states, respectively. Complexes in their excited states are
generally stronger reductants and oxidants than their
ground-state counterparts. A larger value of E0,0 represents
both stronger photoreducing and photooxidizing proper- Figure 1 Example of a reversible cyclic voltammogram
ties. However, the value of E0,0 should be sufficiently low
that the excited state can be accessed upon UV or visible-
light irradiation since it represents the minimum amount of
energy that is required to access that state.
The value of E0,0 can be estimated in a few different
ways, and it is normally expressed in electron volts (eV)
when used to calculate the excited-state redox potentials,
as discussed in a later section. It can be determined spectro-
scopically from the wavelength at the intersection point of
the normalized UV–vis absorption spectrum and the pho-
toluminescence spectrum of the complex measured at
room temperature.33 For complexes that do not display
room-temperature emission or do not have a crossing point
between the absorption and emission spectra due to large Figure 2 Example of an irreversible cyclic voltammogram; the arrows
Stokes shift (most likely to occur for triplet excited states), indicate the direction of the potential scan
the maximum wavelength at the first vibronic peak of the

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Synlett Y. Wu et al. New Tools

*PS enced to the SCE. They are either reported with respect to
the SCE reference electrode from the original work, or are
*E r e –

corrected from the reported experimental conditions by us-

–
+
ed

e
–
*E
hν E0,0 ing well-established conversions.43,44

ox
+ e– – e–
PS– PS PS+
Eox
Ered
Excited-State Redox Potentials
Scheme 1 Modified Latimer diagram showing the ground-state and
excited-state redox processes of a photosensitizer The photoreducing and photooxidizing abilities of a PS
are dictated by its excited-state redox potentials. These po-
For a reversible redox wave, the values of Eox and Ered are tential values refer to the one-electron redox reaction of the
equal to the half-wave potential (E1/2) calculated by using photoexcited PS (*PS), as shown in Scheme 1. Typically, the
Equation 1, where Epc and Epa are the cathodic and anodic excited-state reduction potential [*Ered, or *E(*PS/PS–)] and

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peak potentials respectively, i.e. the potential where the excited-state oxidation potential [*Eox, or *E(PS+/*PS)] are
maximum current of the redox wave is achieved (Figures 1 not directly measured and, instead, are calculated by using
and 2). both the excited-state energy and the standard ground-
state redox potentials, as described in Equation 2 and Equa-
1
E1/2 = × (Epc + Epa) tion 3, respectively. These calculations omit the change in
2
entropy between the ground state and the excited state, as
Equation 1 Calculation of the half-wave potential well as the Coulombic impact of charge separation due to
differences in the solvent. Note that although predictions of
Irreversible oxidation and/or reduction waves imply E0,0 and excited-state redox potentials contain some inher-
that the redox process is followed by a chemical reaction, ent uncertainty, they still provide useful thermodynamic
such as decomposition of the complex or coordination to a evaluations for predicting the redox behavior of a PS in its
solvent molecule. Irreversible electrochemical behavior can excited state. Although it is far less common to do so, *Ered
be detrimental in catalytic applications, as it suggests that and *Eox can also be determined by using phase-modulated
the one-electron reduced and/or oxidized state of the PS is voltammetry, a method in which the redox potentials of a
chemically unstable. In this case, the cathodic and anodic molecular species at its excited state are measured by using
peak potentials (Epc and Epa, respectively) are used to assign an electrochemical cell equipped for light irradiation.45
Ered and Eox, respectively. However, it should be considered Photosensitizers with a more-positive value of *Ered have
that the peak potentials do not represent thermodynamic stronger photooxidizing power, whereas those with a more
redox potentials and that they vary on changing such ex- negative value of *Eox demonstrate stronger photoreducing
perimental conditions as the solvent or the scan rate. The ability.
onset potential (Eonset), which represents the potential
where the initial increase of current appears (Figure 2), has *Ered = Ered + E0,0 (Photooxidant)

also been used in estimations of excited-state redox poten- Equation 2 Calculation of the excited-state reduction potential
tials.40 An alternative method is to use the inflection-point
potential (Ei) to calculate the excited-state potential for ir- *Eox = Eox – E0,0 (Photoreductant)

reversible redox events, a method developed by Vullev et Equation 3 Calculation of the excited-state oxidation potential
al.41,42
Most PSs are studied under nonaqueous conditions, and
the electrochemical potentials are usually either referenced The PS in its excited state can be a potential photore-
against the ferrocenium/ferrocene (Fc+/Fc) redox couple ductant and/or photooxidant, and can engage in bimolecu-
through addition of ferrocene as an internal reference lar SET processes to produce a reactive intermediate species
during the CV experiment, or are referenced against the sat- that initiates the targeted photochemical reaction. When
urated calomel electrode (SCE). Although IUPAC recom- used as a photoreductant, the PS will reduce an electron ac-
mends the use of the Fc+/Fc reference for nonaqueous elec- ceptor (EA) through an oxidative quenching mechanism.
trochemistry,39 the SCE reference electrode has become Conversely, a PS functioning as a photooxidant will oxidize
popular in the field of organic (photo)redox catalysis. an electron donor (ED), and the photocatalytic reaction will
Therefore, to facilitate simple comparison to many other re- proceed through a reductive quenching cycle. The EA/ED
views and resources in this field, the ground-state and ex- can be an organic substrate, a sacrificial redox reagent, or a
cited-state redox potentials summarized here are refer- transition-metal or organic complex that acts as a synergis-

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Synlett Y. Wu et al. New Tools

tic catalyst. Thermodynamically speaking, the value of *Eox aromatic functionalities, visible-light PSs are desirable and
should be more negative than the reduction potential of EA permit selective excitation of the PS in photocatalytic appli-
[E(EA/EA–)] for the PS to reduce an EA, whereas *Ered should cations.
be more positive than the oxidation potential of the ED
[E(ED+/ED)] for the PS to be considered strong enough to Excited-State Lifetime
oxidize an ED. Photosensitizers can be quenched by a sacri-
ficial reductant or oxidant when there is an insufficient The excited-state lifetime (τ) is another relevant consid-
thermodynamic driving force to act directly on the organic eration when evaluating a PS for photoredox catalysis. An
substrate or catalyst, resulting in a net redox change for the ideal PS in photocatalysis should exhibit a long-lived excit-
catalytic cycle and the generation of byproduct(s) from the ed state to provide time for bimolecular SET or energy
sacrificial reagent. Designing PSs with strong photoreduc- transfer to prevail over the inherent radiative or nonradia-
ing and photooxidizing power is still highly desirable to en- tive decay pathways of the excited state. A lifetime lower

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sure efficient SET processes and to improve the catalytic re- than 1 ns [decay rate constant (kr) ≥ 109 s–1] indicates that
activity. As a useful reference, the ground-state electro- the *PS will decay faster than the diffusion limit (~ 109 M–
1 –1 47,48
chemical potentials of a variety of common organic s ), precluding any bimolecular reactivity. Triplet sen-
substrates and sacrificial redox reagents can be found in the sitizers typically show τ at a scale of hundreds of nanosec-
literature.32,46 In general, careful evaluation of redox prop- onds to milliseconds, several orders of magnitude longer
erties of the PS and reaction partners is essential to the suc- than those of singlet PSs, due to the spin-forbidden nature
cess of photochemical reactions. of the T1→S0 transition. A persistent challenge in designing
transition-metal-based PSs is that their ligand-field d–d
Absorption Maximum Wavelength at the Lowest-En- states can be populated when they are lower in energy
ergy Absorption Peak than, or thermally accessible from, the desired charge-
transfer state, leading to nonradiative thermal deactivation
Analyzing the UV–vis absorption profile is important in and short-lived excited states. Overall, the design of PSs
choosing an appropriate light source for photoexcitation of with prolonged excited-state lifetimes remains an active
the PS. A figure of merit is the peak wavelength of the low- area of study in photoredox catalysis.
est-energy (longest wavelength) absorption band (max).
Note that for many PSs, particularly those from the cyclo- Summary of Photophysical and Electrochemical
metalated iridium family, it is common to have several Properties of Photosensitizers
overlapping low-energy absorption bands without a clear
maximum. In these cases, the quoted max is often in the UV The key photophysical and electrochemical properties
region, but there is still sufficient visible absorption to per- of PSs are listed in Tables 1–9. Organic dyes (Table 1) and
mit excitation by visible light. For solar-energy harvesting, polypyridyl complexes of Ru and cyclometalated Ir com-
e.g. in solar fuels catalysis, it is desirable for absorption to plexes (Table 2) make up the majority of PSs highlighted in
occur over the entire solar spectrum to maximize light cap- this review, because these are the most prominent in pho-
ture. When using an artificial light source, as is frequently tocatalytic organic synthesis. In the case of organic PSs, the
done in organic photoredox catalysis, there should be some excited-state energy, lifetime, and excited-state redox po-
overlap between the absorption spectrum of the PS and the tentials for both singlet and triplet excited states are includ-
emission range of the light source. It is preferable to use ed if both items of data are available. For organic PSs, the
light sources that activate the lowest-energy absorption to SET process from the singlet excited state can take place be-
permit selective photoexcitation of the PS. This can avoid fore generation of the triplet excited state by ISC, due to the
undesired activation of other reaction components or inter- relatively low ΦISC (quantum yield of ISC) for organic mole-
mediates by high-energy light sources, potentially compli- cules.49 Other transition metal PSs are categorized on basis
cating the reaction mechanism and compromising the reac- of the identity of the metal, and are summarized in Tables
tion selectivity and catalyst durability. Because most organ- 3–9. In all tables, n/a indicates data not available; s, data for
ic substrates absorb in the UV range, especially those with singlet excited state (S1); and t, data for triplet excited state
(T1).

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Synlett Y. Wu et al. New Tools

Table 1 Summary of Photophysical and Electrochemical Properties of Organic Photosensitizers

Cl
OAc
Cl Cl
COOH COOH AcO
COOH OAc
Br Br Cl COOH
I I OAc
HO O O N O N N N O
HO O O
Br Br HO O O
N
I I N
O

max (nm) 539 450 549 550 443

τ (s) 24t; 0.00266s 0.0047s 0.0005s 0.00245s 68t; 0.0057s
E0,0 (eV) 1.89t; 2.31s 1.94t; 2.42s 1.77t; 2.17s 1.80t; 2.22s 2.07t; 2.58s
red
E (V vs. SCE) –1.06 –1.22 –0.78 –0.96 –0.82

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Eox (V vs. SCE) +0.78 +0.70 +1.09 +0.91 n/a
red t s t s t s t s
*E (V vs. SCE) +0.83 ; +1.25 +0.72 ; +1.20 +0.99 ; +1.39 +0.84 ; +1.26 +1.25t; +1.76s
ox t s t s t s t s
*E (V vs. SCE) –1.11 ; –1.53 –1.24 ; 1.72 –0.68 ; –1.08 –0.89 ; –1.31 n/a
Refs. 50–52 51–53 51,54–56 14,51 57
O O O
O
Cl CN Cl Cl
N

Cl CN Me
Cl Cl ClO4
Me2N NMe2
O O O

max (nm) 365 410 400 510 320–470

τ (s) 3t 0.0032s 2.4t 3.5t 0.037s
E0,0 (eV) 2.70 ; 2.98
t s
2.73 ; 2.88
t s
2.67 ; 3.29
t s
2.70 t
2.75s
Ered (V vs. SCE) –2.20 –0.96 +0.51 +0.02 –0.43
E (V vs. SCE)
ox
+0.86 n/a n/a n/a n/a
*Ered (V vs. SCE) +0.50t; +0.78s +1.77t; +1.92s +3.18t; +3.8s +2.72t +2.32s
*Eox (V vs. SCE) –1.84t; –2.20s n/a n/a n/a n/a
Refs. 14,58–60 61–65 66,67 68 69–71
Me Me Me
Me Me

Me Me Me
Me Me Me Me Me Me
Me
MeO OMe
MeO OMe
N tBu N tBu N OMe
N MeO N OMe MeO
Me ClO4 BF4 BF4 BF4
BF4

max (nm) 425 420 466 407 412

τ (s) 30t; 0.006s 0.0144 0.0187 τ1 = 0.003a τ1 = 0.0013 (92%)a
τ2 = 0.0101 τ2 = 0.0089 (8%)
E0,0 (eV) 2.37t; 2.68s 2.67 2.47 2.72 2.46
Ered (V vs. SCE) –0.49 –0.59 –0.57 –0.71 –0.84
Eox (V vs. SCE) +1.88 n/a n/a n/a n/a
*Ered (V vs. SCE) +1.88t; +2.19s +2.08 +1.90 +2.01 +1.62
*Eox (V vs. SCE) –0.49t; –0.80s n/a n/a n/a n/a
Refs. 72–75 76 76 76 76

Me CN NC CN
CN
N N
N N
Me Me N
MeO OMe NC CN
CN N N N N
CN
MeO N OMe N N
N
BF4
MeO
OMe

max (nm) 414 422 379 369 492

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Synlett Y. Wu et al. New Tools

τ (s) τ1 = 0.0013a 0.0149 5.1t; 0.4s 5.03 1.46

τ2 = 0.0123
E0,0 (eV) 2.47 1.81t; 2.90s 2.59t; 2.64s 2.45t 2.34t
Ered (V vs. SCE) – 0.82 –0.91 –1.21 –1.16 –1.02
ox
E (V vs. SCE) n/a n/a +1.52 n/a n/a
*Ered (V vs. SCE) +1.65 +0.90t; +1.99s +1.38t; +1.43s +1.29t +1.32
*Eox (V vs. SCE) n/a n/a –1.07t; –1.12s n/a n/a
Refs. 76 14,77 78–81 78,80 78,80
tBu tBu

N N N
N N
NC CN NC CN F F
NC CN NC CN

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tBu N N tBu N
N N N N
N N N N
Cl CN
Cl F

tBu tBu
tBu tBu

max (nm) 468 n/a n/a n/a n/a

τ (s) 2.9 0.0069 0.0115 0.0042 0.0042
E0,0 (eV) 2.53 2.72 2.65 2.84 2.68
red
E (V vs. SCE) –1.32 –1.16 –1.41 –1.92 –1.59
Eox (V vs. SCE) +1.22 +1.79 +1.31 +1.24 +1.30
*Ered (V vs. SCE) +1.21 +1.56 +1.24 +0.92 +1.09
*Eox (V vs. SCE) –1.31 –0.93 –1.34 –1.60 –1.38
Refs. 82,83 84 84 84 84
NC CN N
Cl

Me2N S NMe2
N N
N N

O O
S

BF4

max (nm) 374 665 n/a 324 417

τ (s) 166 77t; 0.001s τ1 = 0.00081 (54%)a 0.0029 10t; 0.0029s
τ2 = 0.0023 (46%)
E0,0 (eV) 2.63t 1.85t; 1.86s 2.4t; 2.8s 2.69t 2.30t; 2.83s
red
E (V vs. SCE) –1.45 –0.30 n/a n/a –0.32
Eox (V vs. SCE) +1.47 +1.13 +0.68 +0.58 n/a
red t t s
*E (V vs. SCE) +1.18 +1.55 ; +1.56 n/a n/a +1.98t; +2.51s
ox t t s t s t
*E (V vs. SCE) –1.16 –0.72 ; –0.73 –1.7 ; –2.1 –2.11 n/a
Refs. 78,85 14,51,86 14,87,88 89,90 77,91

OMe CF3 CN

N N N
N
N

N N N
N

OMe CF3 CN

max (nm) 373 370 367 322 343

τ (s) n/a n/a n/a n/a 4.3t
E0,0 (eV) 2.31t 2.34t 2.37t 2.21t 1.9t
red
E (V vs. SCE) n/a n/a n/a n/a n/a

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Synlett Y. Wu et al. New Tools

Eox (V vs. SCE) –0.05 0.00 +0.13 +0.16 +0.21

red
*E (V vs. SCE) n/a n/a n/a n/a n/a
*Eox (V vs. SCE) –2.36t –2.34t –2.24t –2.06t –1.69t
Refs. 92 92 92 92 93,94

Ph iPr O O iPr

N N
N
iPr O O iPr
Ph N
O
Me
Ph Ph

max (nm) n/a 388 527

τ (s) n/a 480t 0.0038s

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E0,0 (eV) 3.02 2.45t 2.34s
E red
(V vs. SCE) n/a n/a –0.37
Eox (V vs. SCE) +1.10 +0.65 +1.65
*Ered (V vs. SCE) n/a n/a +1.97s
*E (V vs. SCE)
ox
–1.92 –1.80 t
–0.69s
Refs. 95 89,93,96 97–100
Ph Ph Et H
N tBu tBu
BF4
N N
nPr nPr
N N N
C Me2N NMe2 Me2N NMe2

N
Ph Ph
O O
N

tBu tBu

max (nm) 616 375 471 388 n/a

s
τ (s) 0.0055 0.009 0.031 0.017 n/a
E0,0 (eV) 1.93 2.71s 2.2 3.02 3.05
Ered (V vs. SCE) –0.78 n/a n/a n/a n/a
ox b c
E (V vs. SCE) +1.32 +0.76 +0.78 +0.27 +0.29
*Ered (V vs. SCE) +1.15 n/a n/a n/a n/a
ox s
*E (V vs. SCE) –0.61 –1.95 –1.42 –2.75 –2.76
Refs. 101–104 105 106 107,108 109

O O
O F O O

O O O O

Br OTf

max (nm) 421 421 411 421 413

τ (s) 0.00144 0.00207 0.00386 0.00149 0.00081
E0,0 (eV) 3.02 3.15 3.22 3.16 3.20
red
E (V vs. SCE) –1.74 –1.68 –1.67 –1.61 –1.55
Eox (V vs. SCE) +1.75 +1.81 +1.80 +1.78 +1.86
*Ered (V vs. SCE) +1.28 +1.47 +1.55 +1.55 +1.65
ox
*E (V vs. SCE) –1.27 –1.34 –1.42 –1.38 –1.34
Refs. 110 110 110 110 110

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Synlett Y. Wu et al. New Tools

O O O O
O

O O O O
O

OMe OH
TMS Ph

CN

max (nm) 462 461 426 434 427

τ (s) 0.00778 0.0085 0.00253 0.00334 0.00305
E0,0 (eV) 2.97 2.89 3.13 3.12 3.14
Ered (V vs. SCE) –1.76 –1.89 –1.71 –1.70 –1.58

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Eox (V vs. SCE) +1.47 +1.44 +1.73 +1.64 +1.69
red
*E (V vs. SCE) +1.21 +1.00 +1.42 +1.42 +1.56
*Eox (V vs. SCE) –1.50 –1.45 –1.40 –1.48 –1.45
Refs. 110 110 110 110 110

MeO CF3
N CN
S
O
O N
S
MeO N CN
O
O

OMe
Cz

max (nm) 449 459 448 341 338

τ (s) 0.00421 0.00249 n/a 0.0017 0.017
E0,0 (eV) 3.08 3.12 2.01t 3.23 2.73
red
E (V vs. SCE) –1.65 –1.59 –1.45 n/a n/a
Eox (V vs. SCE) +1.44 +1.35 +1.37 +0.96 +0.97
*Ered (V vs. SCE) +1.43 +1.53 +0.91t n/a n/a
ox
*E (V vs. SCE) –1.64 –1.77 –1.17t –2.27 –1.76
Refs. 110 110 111–113 114 114
F 3C CF3 F3C CF3
CF3 F3C CF3

N N
N
N

Ph Ph
N N tBu tBu

max (nm) 348 338 358 360

τ (s) 0.0027, 0.0161 0.0179 0.0172 0.0168
E0,0 (eV) 2.50 2.62 2.63 2.63
red
E (V vs. SCE) n/a n/a n/a n/a
Eox (V vs. SCE) +0.69 +1.02 +0.94 +0.98
*Ered (V vs. SCE) n/a n/a n/a n/a
*Eox (V vs. SCE) –1.81 –1.60 –1.69 –1.65
Refs. 114 114 114 114

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Synlett Y. Wu et al. New Tools

O R
MeO P Ph N N
Ph
N O N N
R

R – H Et Ph OMe CF3

max (nm) 378 414 412 408 410 408

τ (s) n/a n/a n/a n/a n/a n/a
E0,0 (eV) 2.84 2.09t; 2.11t; 2.58s 2.14t; 2.57s 2.13t; 2.56s 2.15t; 2.55s
2.57s

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Ered (V vs. SCE) n/a n/a n/a n/a n/a n/a
E (V vs. SCE)
ox
+1.55 +0.26 +0.57 +0.68 +0.65 +0.76
*Ered (V vs. SCE) n/a n/a n/a n/a n/a n/a
ox t t t s t s
*E (V vs. SCE) –1.29 –1.60 ; –1.71 ; – –1.61 ; –1.89 –1.65 ; –1.91 –1.56t; –1.79s
–2.31s 2.01s
Refs. 115–117 118,119 118,119 118,119 118,119 118,119
a
Biexponential.
b
Redox potentials were originally referenced vs. Fc+/Fc in MeCN and are corrected by adding 0.40 V for referencing against the SCE.
c
Redox potentials were originally referenced vs. Fc+/Fc in CH2Cl2 and are corrected by adding 0.46 V for referencing against the SCE.

Table 2 Summary of Photophysical and Electrochemical Properties of Ru- and Ir-Based Photosensitizers

2+ tBu N
2+ 2+ 2+

N N 2+
tBu N N N
N N N N N tBu
N N N
Ru Ru N N
N N Ru
N N N N Ru Ru N N
N N N N N N N N N
N N
tBu tBu
N

tBu

max (nm) 452 447 458 459 443

τ (s) 1.1 0.5 0.875 0.99 0.74
E0,0 (eV) 2.10 2.18 2.06 n/a 2.12
red
E (V vs. –1.33 –1.36 –1.43 n/a –0.80
SCE)
Eox (V vs. +1.29 +1.26 +1.14 n/a +1.86
SCE)
*Ered (V +0.77 +0.82 +0.63 n/a +1.45
vs. SCE)
*Eox (V vs. –0.81 –0.87 –0.92 n/a –0.26
SCE)
Refs. 7,120–122 120,123 124,125 126,127 120,128,129

N F F F
2+ CF3
N N
N N N N
N N N F F F F3C
Ru Ir Ir Ir Ir
N N N N N N N N N N
N
N
N
N F F F CF3

max (nm) 454 376 378 380 372

τ (s) 0.131 1.9 1.6 2.04 2.16
E0,0 (eV) 1.9 2.58 2.22 2.86 2.76

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Synlett Y. Wu et al. New Tools

Ered (V vs. –0.91 –2.23 –1.87 –2.18 –2.17

SCE)
Eox (V vs. +1.69 +0.77 +0.94 +0.96 +1.06
SCE)
*Ered (V +0.99 +0.35 +0.36 +0.68 +0.59
vs. SCE)
*Eox (V vs. –0.21 –1.88 –1.28 –1.90 –1.7
SCE)
Refs. 130 131–133 134–136 132,135 132,135

R2
R1
R4
R3 R3
N

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4
R
Ir
R1
N N

R2 R2
R1
R3
R3

R R1 = t-Bu; R2 = t-Bu; R3 = t-Bu; R4 = t-Bu; R2 = OMe; R3 = OMe; R4 = OMe; R1 = H;

R2 = R3 = R4 = H R1 = R3 = R4 = H R1 = R2 = R4 = H R1 = R2 = R3 = H R1 = R3 = R4 = H R1 = R2 = R4 = H R1 = R2 = R3 = H R2 = R3 = R4 =
OMe
max (nm) 373 382 384 382 381 397 359 396
τ (s) n/a n/a n/a 1.97 n/a 2.86 2.24 n/a
E0,0 (eV) 2.58 2.58 2.52 2.56 2.59 2.40 2.64 2.42
Ered (V vs. –2.30 n/a –2.26 –2.33 n/a –2.21 –2.34 n/a
SCE)
Eox (V vs. +0.68 +0.64 +0.60 +0.60 +0.59 +0.53 +0.70 +0.34
SCE)
*Ered (V +0.28 n/a +0.26 +0.23 n/a +0.19 +0.26 n/a
vs. SCE)
*Eox (V vs. –1.89 –1.94 –1.92 –1.96 –2.00 –1.87 –1.95 –2.07
SCE)
Refs. 131 131 131 131,132 131 131,132 131,132 131

+
R1
R2
N
N
Ir
N
N
R4
R3

R R1 = R3 = CF3; R1 = R3 = Me; R1 = R3 = F; R1 = R2 = R3 R1 = R3 = H; R1 = R2 = R3 = H; R4 = NH2 R1 = R3 = R1 = R3 = H;

R2 = R4 = H R2 = R4 = H R2 = R4 = H = R4 = Me R2 = R4 = NH2 Me; R2 = R4 = N-pyr-
R2 = R4 = rolidinyl
NH2
max n/a n/a n/a n/a n/a n/a n/a n/a
(nm)
τ (s) 0.002 0.868 0.186 1.047 1.823 0.751 1.866 1.826
E0,0 (eV) 2.03 2.49 2.40 2.59 2.65 2.57 2.64 2.64
red
E (V –0.77 –1.41 –1.26 –1.52 –1.78 –1.52 –1.91 –1.74
vs. SCE)
Eox (V n/a +1.35 +1.40 +1.28 +1.15 +1.22 +1.14 +1.21
vs. SCE)
*Ered (V +1.26 +1.08 +1.14 +1.07 +0.87 +1.05 +0.73 +0.90
vs. SCE)
*Eox (V n/a –1.14 –1.00 –1.31 –1.50 –1.35 –1.50 –1.43
vs. SCE)
Refs. 42 42 42 42 42 42 42 42

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F F F +
O3S SO3 O3S
N N O3S SO3 SO3
N N
N

Ir F F F N
Ir Ir Ir
N N Ir
N N N N N N
N
N

F F F
SO3
SO3 Na SO3 SO3

max n/a n/a n/a n/a 420

(nm)
τ (s) 1.56 1.62 2.16 2.11 0.31
E0,0 (eV) 2.50 2.65 2.76 2.81 2.66

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red
E (V n/a n/a n/a n/a –2.05
vs. SCE)
Eox (V +0.56 +0.76 +0.91 +1.05 +1.25
vs. SCE)
*Ered (V n/a n/a n/a n/a +0.61
vs. SCE)
*Eox (V –1.94 –1.89 –1.85 –1.76 –1.41
vs. SCE)
Refs. 137 137–139 137 137 140–142

+ CF3 + + +
CF3 + CF3 CF3
F F F
F F
CF3
tBu N CF3 tBu
N N N N
N F N N N
F N F F
Ir Ir Ir Ir
Ir F F
N F N N N
F N
N N N
tBu N CF3 tBu
N
F F F
CF3 F CF3 CF3
F CF3
CF3

max 410 n/a n/a n/a 380

(nm)
τ (s) 0.557 0.28 n/a n/a 2.3
E0,0 (eV) 2.17 2.37 2.77 2.44 2.90
Ered (V –1.51 –0.69 –1.16 –0.79 –2.01
vs. SCE)
Eox (V +1.21 +1.94 +1.87 +1.93 +1.69
vs. SCE)
*Ered (V +0.66 +1.68 +1.61 +1.65 +0.89
vs. SCE)
*Eox (V –0.96 –0.43 –0.90 –0.51 –1.21
vs. SCE)
Refs. 25,126,143 144 144 144 145,146
OMe NMe2
+ +
CF3
F
S N OMe
N OMe N
N N
N
N N N
N Ir
F Ir
Ir Ir Ir
N
F N N N
N N
OMe N N
N OMe
N
S
F
CF3
OMe NMe2

max 412 437 475 435 488

(nm)
τ (s) 2.28 3.90 0.40 0.52 n/a
E0,0 (eV) 2.69 2.13 2.40 2.40 2.30
Ered (V –1.37 –1.43a n/a n/a n/a
vs. SCE)

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Synlett Y. Wu et al. New Tools

Eox (V +1.69 +1.03a +0.25 +0.29 +0.17

vs. SCE)
*Ered (V +1.32 +0.70 n/a n/a n/a
vs. SCE)
*Eox (V –1.00 –1.10 –2.20 –2.10 –2.10
vs. SCE)
Refs. 147,148 149 35 35 35

N N N NMe2
N N
N
N N tBu
N tBu N Ir
Ir Ir Ir tBu
Ir tBu N
N N N
N N NMe2
N N
N

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N

max 500 536 485 506 494

(nm)
τ (s) 0.53 0.63 0.15 0.35 0.51
E0,0 (eV) 2.30 2.20 2.40 2.00 2.30
E (V
red
n/a n/a n/a n/a n/a
vs. SCE)
Eox (V +0.30 +0.07 +0.27 +0.01 +0.13
vs. SCE)
*Ered (V n/a n/a n/a n/a n/a
vs. SCE)
*Eox (V –2.00 –2.10 –2.10 –2.00 –2.20
vs. SCE)
Refs. 35 35 35 35 35

+
N N
N N N
R NMe2
N nBu
N N N N
Ir Ir Ir
N
N N N Ir
N R N N NMe2 N
N N
N
N nBu

R R = Me R = NMe2 R = OEt – – –
max 460 511 456 308 400 416
(nm)
τ (s) 0.20 0.76 2.0 n/a 0.35 n/a
E0,0 (eV) 2.40 2.30 2.40 2.30 2.20 2.74
Ered (V n/a n/a n/a n/a n/a –2.03
vs. SCE)
Eox (V +0.33 +0.14 +0.43 +0.30 +0.15 +1.04
vs. SCE)
*Ered (V n/a n/a n/a n/a n/a +0.71
vs. SCE)
*Eox (V –2.10 –2.20 –2.00 –2.00 –2.00 –1.70
vs. SCE)
Refs. 35,150 35,150 35,150 35 35 40

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Synlett Y. Wu et al. New Tools

+ + + + +

S Me N N
N Me nBu
N N N
N S N
N nBu nBu
N N N N
Ir Ir Ir
N N N N
N
Ir Ir
N N N N N
N Me
S Me N nBu
N
N N
N nBu N nBu
S

max 405 421 421 494 485

(nm)
τ (s) n/a n/a 28.7 n/a n/a

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E0,0 (eV) 2.43 2.47 2.47 2.15 2.10
Ered (V –1.76 –1.97 –1.96 –1.54 –1.66
vs. SCE)
Eox (V +0.84 +0.96 +0.96 +0.82 +0.88
vs. SCE)
*Ered (V +0.67 +0.50 +0.51 +0.61 +0.44
vs. SCE)
*Eox (V –1.59 –1.51 –1.51 –1.33 –1.22
vs. SCE)
Refs. 40 40 40 40 40

+
+ CF3 + + +
S Hex Hex
N
S N
N nBu
nBu S N
N nBu
N nBu
N N N
nBu N Hex
N N Hex N
N Ir
Ir N Ir
N N Ir Hex N
N Hex
Ir N N
N N nBu
N N nBu
N nBu
N N nBu Hex
nBu S Hex N
S N

CF3

max 436 447 467 421 436

(nm)
τ (s) 6.4 3.2 n/a n/a 96.1
E0,0 (eV) 2.50 2.50 2.25 2.45 2.24
Ered (V –1.73 –1.52 –1.67 –1.97 –1.80
vs. SCE)
Eox (V +1.17 +1.23 +0.89 +0.96 +0.98
vs. SCE)
*Ered (V +0.77 +1.03 +0.58 +0.48 +0.44
vs. SCE)
*Eox (V –1.33 –1.27 –1.36 –1.49 –1.26
vs. SCE)
Refs. 40 40 40 40 40

+ +
+ + +
O
NH2
NMe2
N
N N N N
N
N N N
Ir N
Ir N
N N Ir
N N
Ir Ir N N
N N
N N N N

max 460 459 459 446 452

(nm)

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Synlett Y. Wu et al. New Tools

τ (s) 0.9 1.0 1.6 2.1 2.2

E0,0 (eV) 2.61 2.63 2.65 2.69 2.72
Ered (V –1.65 –1.74 –1.73 –1.73 –1.76
vs. SCE)
Eox (V +1.23 +1.21 +1.23 +1.22 +1.20
vs. SCE)
*Ered (V +0.96 +0.89 +0.93 +0.97 +0.96
vs. SCE)
*Eox (V –1.38 –1.42 –1.42 –1.47 –1.52
vs. SCE)
Refs. 151 151 151 151 151

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Ph2N + + + + +
NMe2 tBu NMe2 tBu
N N
N N N

N N N
Ir Ir Ir
N N N
N N N N
N N
N
N Ir
N N
N
Ir
N N

max 494 474 485 430 494

(nm)
τ (s) 1.8 3.0 0.2 2.4 0.1
E0,0 (eV) 2.15 2.31 2.42 2.71 2.46
Ered (V –1.16 –1.27 –1.33 –1.71 –1.35
vs. SCE)
Eox (V +0.91 +1.00 +1.37 +1.26 +1.37
vs. SCE)
*Ered (V +0.99 +1.04 +1.09 +1.00 +1.11
vs. SCE)
*Eox (V –1.24 –1.31 –1.05 –1.45 –0.97
vs. SCE)
Refs. 151 151 151 151 151

F F + F F +
+ F +
+ F F

tBu tBu tBu tBu

N N F
N N N N N N tBu
Ir Ir Ir Ir N N
N N N N N N N N Ir
N N
tBu tBu tBu tBu
Cl tBu Cl tBu Cl tBu Cl tBu tBu
Cl tBu

max 465 450 455 450 436

(nm)
τ (s) 3.02 3.17 3.77 3.87 3.05
E0,0 (eV) 2.31 2.36 2.36 2.41 2.49
Ered (V –1.23 –1.17 –1.21 –1.18 –1.19
vs. SCE)
Eox (V +1.61 +1.70 +1.69 +1.87 +1.88
vs. SCE)
*Ered (V +1.07 +1.19 +1.15 +1.22 +1.30
vs. SCE)
*Eox (V –0.70 –0.66 –0.67 –0.54 –0.61
vs. SCE)
Refs. 152 152 152 152 152

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F F + F
+ F + F +
F F F
F

tBu F tBu
F N tBu N
tBu N N
N Ir N N Ir
N OCH3
Ir OCH3 Ir
N N N N
N N N N
tBu tBu
CN tBu tBu CN tBu
tBu CN tBu
Cl tBu

max 435 430 337 428

(nm)
τ (s) 3.15 3.35 9.93 3.50
E0,0 (eV) 2.49 2.54 2.64 2.58
Ered (V –1.14 –1.17 –1.17 –1.17
vs. SCE)

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Eox (V +1.83 +1.95 +2.00 +1.73, +2.01
vs. SCE)
*Ered (V +1.35 +1.37 +1.47 +1.42
vs. SCE)
*Eox (V –0.66 –0.59 –0.64 –0.57
vs. SCE)
Refs. 152 152 152 152
a
Redox potentials were originally reported vs. the Ag/AgCl reference potential in MeCN, where the Fc /Fc redox couple appears at 0.56 V. Potentials were initially +

converted into the Fc+/Fc reference and then corrected by adding 0.40 V for referencing against the SCE.

Table 3 Summary of Photophysical and Electrochemical Properties of Cu Photosensitizers

MeO
+ + +
+
Ph Me Ph2 iPr Ph2 Ph iPr Ph2
P P P
Ar N N N

N Cu O Cu O Cu O
N
N N N
Cu
Ph2P Ph2P Ph2P
N N Ph Me iPr Ph iPr

Ar

Ar = 4-MeOC6H4

MeO

max (nm) n/a 387 380 385

τ (s) 0.27 n/a n/a n/a
E0,0 (eV) 2.05 2.64 2.77 2.70
Ered (V vs. SCE) n/a –1.59 –1.73 –1.66
Eox (V vs. SCE) +0.62 +1.27 +1.34 +1.35
*Ered (V vs. SCE) n/a +1.05 +1.04 +1.04
ox
*E (V vs. SCE) –1.43 –1.37 –1.43 –1.35
Refs. 153,154 155 155 156

+ + + +
Ph2
Ph2P P Ph2
Ph N N
N P
O Cu O O N
N C Cu
O
N N Cu O
Cu P
Ph2P Ph2P N
N Ph
C O Ph2P
Ph N

max (nm) n/a n/a n/a n/a

τ (s) 17 0.72 0.41 0.82
E0,0 (eV) 2.57 2.19 2.23 2.27
Ered (V vs. SCE) n/a n/a n/a –1.64
Eox (V vs. SCE) +0.69 +1.23 +1.15 +1.25

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*Ered (V vs. SCE) n/a n/a n/a +0.63

ox
*E (V vs. SCE) –1.88 –0.96 –1.08 –1.02
Refs. 157 158 158 159

+ +
+ + MeO

Ph2 N Ph2
N Ph2 N Ph2 N P
P P P
Cu Cu
Cu Cu
Ph2 P
N Ph2 P
N Ph2 P N Ph2 P N

MeO

max (nm) 394 387 382 375

τ (s) 0.0031 2.188 0.004 0.00264
E0,0 (eV) 2.38 2.38 2.38 2.38

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Ered (V vs. SCE) n/a n/a n/a n/a
ox
E (V vs. SCE) +0.78 +0.75 +0.87 +0.93
*Ered (V vs. SCE) n/a n/a n/a n/a
*Eox (V vs. SCE) –1.60 –1.64 –1.52 –1.45
Refs. 160 160 160 160

+ p-Tol +
tBu + +
N N
N Ph2 N Ph2
P N Ph2 N Ph2 P
P P
Cu Cu
Cu Cu
N Ph2 P N Ph2 P
N Ph2 P N Ph2 P
tBu

max (nm) 379 412 472 378

τ (s) 0.00219 0.00278 0.004 0.00240
E0,0 (eV) 2.38 2.38 2.38 2.38
Ered (V vs. SCE) n/a n/a n/a n/a
ox
E (V vs. SCE) +0.91 +0.83 +0.51 +0.71
*Ered (V vs. SCE) n/a n/a n/a n/a
ox
*E (V vs. SCE) –1.47 –1.55 –1.87 –1.67
Refs. 160 160 160 160

p-Tol + + +
p-Tol +
N N N N
Ph2 N Ph2 Ph2P
N P Ph2P
P N
Cu N
Cu
O
N Ph2 P N Ph2 P Cu O Cu
N N
Ph2P Ph2P

max (nm) 410 406 443 445

τ (s) 0.00311 0.00358 0.274 0.393
E0,0 (eV) 2.38 2.38 1.87 1.90
Ered (V vs. SCE) n/a n/a n/a n/a
ox
E (V vs. SCE) +0.70 +0.66 +0.60 +1.14
*Ered (V vs. SCE) n/a n/a n/a n/a
*Eox (V vs. SCE) –1.68 –1.72 –1.27 –0.76
Refs. 160 160 160 160

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+ H2N + O
+
NH NH p-FC6H4 S
NH + Ph2P
N Ph2 Ph2
P N O N
P NH
Cu Cu Ph2 O
N Cu
P
N Ph2 P N Ph2 P
Cu N
Ph2P
N Ph2 P

max (nm) 373 381 374 n/a

τ (s) 0.00742 0.00746 0.00895 n/a
E0,0 (eV) 2.30 2.29 2.00 2.24
Ered (V vs. SCE) –0.18 –0.43 –0.04 n/a
Eox (V vs. SCE) +1.07 +0.81 +1.11 +0.38

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*Ered (V vs. SCE) +2.12 +1.87 +1.96 n/a
*Eox (V vs. SCE) –1.23 –1.48 –0.89 –1.86
Refs. 161 161 161 162

+
+ Ph2
N H
Ph2P P
Cu C
N Ph2
Ph2 C N H
Cu O N P N P P
Ph2 Cu C
N Cu Fe C
Ph2P N P
N P
N N Ph2
Ph2 = BH

= BH

max (nm) n/a 464 438 449

τ (s) n/a 0.0027 1.2 1.4
E0,0 (eV) 2.73 2.15 2.45 2.40
Ered (V vs. SCE) –1.96 n/a –1.77a –1.43, –1.64a
Eox (V vs. SCE) +0.8 +0.77 n/a n/a
red
*E (V vs. SCE) +0.77 n/a +0.68 +0.97
*Eox (V vs. SCE) –1.93 –1.38 n/a n/a
Refs. 163 160 164 164
a
Redox potentials were originally reported against the Ag/AgCl reference potential and are corrected by subtracting 0.039 V for referencing against the SCE.44

Table 4 Summary of Photophysical and Electrochemical Properties of Os Photosensitizersa

2+ 2+ 2+
Me
N N Me N
N
N N N N
N Os N
Os Os
N N N N N
Me N
N N Me

max (nm) 640 650 n/a

τ (s) 0.02 0.08 n/a
E0,0 (eV) 1.75 1.8 1.69
Ered (V vs. SCE) –1.41 –1.42 –0.83
ox
E (V vs. SCE) +0.79 +0.86 +1.0
*Ered (V vs. SCE) +0.34 +0.38 +0.86
*Eox (V vs. SCE)) –0.96 –0.94 –0.69
Refs. 165,166 165,166 166

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2+

N
N

R N Os N R

N
N

R H t-Bu O S OMe OMe Br

MeO OMe

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max (nm) 657 n/a n/a n/a n/a n/a n/a n/a n/a
τ (s) 0.269 n/a n/a n/a n/a n/a n/a 0.2 n/a
E0,0 (eV) 1.77 1.8 1.72 1.75 1.74 1.76 1.79 1.75 1.75
red
E (V vs. SCE) –1.24 –1.05 –1.00 –0.87 –0.99 –0.94 –1.01 –0.86 –0.91
Eox (V vs. SCE) +0.94 +1.07 +1.02 +0.99 +1.01 +1.14 +1.10 +1.04 +0.99
*Ered (V vs. SCE) +0.53 +0.75 +0.72 +0.88 +0.75 +0.82 +0.78 +0.89 +0.84
*Eox (V vs. SCE) –0.83 –0.73 –0.70 –0.76 –0.73 –0.62 –0.69 –0.71 –0.76
Refs. 166,167 166 166 166 166 166 166 166,168 166

2+ 2+ 2+
2+
N N N
N N N
F3C N N CF3 N N N
N N N N N
R N Os N R N Os N N Os N N Os N
N N N
N N N N
F3C N N CF3 N N N
N N
N N

R H OMe – – –
max (nm) n/a n/a n/a n/a n/a
τ (s) n/a n/a n/a n/a n/a
E0,0 (eV) 1.77 1.79 1.78 1.71 1.96
Ered (V vs. SCE) –0.80 –0.63 –0.58 –0.98 –1.34
Eox (V vs. SCE) +1.21 +1.33 +1.50 +0.77 +1.21
*Ered (V vs. SCE) +0.97 +1.16 +1.20 +0.73 +0.62
*Eox (V vs. SCE) –0.56 –0.46 –0.28 –0.94 –0.75
Refs. 166 166 166 166 166
a
Redox potentials were originally reported against the Ag/AgCl reference potential and are corrected by subtracting 0.039 V for referencing against the SCE.44

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Table 5 Summary of Photophysical and Electrochemical Properties of Zr Photosensitizers

Ph
Ph
N
N
N Zr N N Zr N
N N Zr N
N Ph
N Ph N
N Ph
N
Ph Ph
Ph

max (nm) 528 471 470

τ (s) 325 412 τ1 = 77, τ2 = 296c

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E0,0 (eV) 2.09 2.19 2.21
Ered (V vs. SCE) –1.60a –1.80b –1.81b
Eox (V vs. SCE) n/a n/a n/a
*Ered (V vs. SCE) +0.49 +0.39 +0.40
*Eox (V vs. SCE) n/a n/a n/a
Refs. 169,170 171 171
a
Redox potentials were originally referenced vs. Fc+/Fc in THF and are corrected by adding 0.56 V for referencing against the SCE.
b
Redox potentials were originally referenced vs. Fc+/Fc in 1,2-difluorobenzene and are corrected by adding 0.46 V for referencing against the SCE.
c
Biexponential.

Table 6 Summary of Photophysical and Electrochemical Properties of Group 6 Photosensitizers

tBu tBu

tBu tBu tBu tBu

N
N N tBu N tBu
N N N
Mo tBu N tBu N
N Mo tBu Cr tBu
N N tBu N tBu
N N N
N N
tBu tBu tBu tBu
tBu tBu tBu tBu

tBu tBu

max (nm) 350–550 350–550 400–600

τ (s) 0.225 τ1 = 1.04 (76%), τ2 = 2.37 (24%)a 0.0022
E0,0 (eV) 2.20 2.20 2.05
Ered (V vs. SCE) n/a n/a n/a
Eox (V vs. SCE) –0.02 –0.08 +0.18b
*Ered (V vs. SCE) n/a n/a n/a
*Eox (V vs. SCE) –2.2 –2.3 –1.87
Refs. 172,173 172 174,175

iPr
iPr iPr iPr
R R
N
N N
iPr iPr
W
iPr iPr
N N
N
R iPr iPr R
iPr iPr

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R H OMe OMe

OMe

OMe OMe

max (nm) 465 n/a n/a n/a n/a

τ (s) 0.122 1.73 1.53 1.65 1.83
E0,0 (eV) 2.28 2.12 2.08 2.14 2.15
red
E (V vs. SCE) n/a n/a n/a n/a n/a
Eox (V vs. SCE) –0.26c –0.22c –0.21c –0.19c –0.19c
*Ered (V vs. SCE) n/a n/a n/a n/a n/a
*Eox (V vs. SCE) –2.54 –2.34 –2.29 –2.33 –2.34

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Refs. 176–178 176 176 176 176

Ph Ph

N N N N N N
R R
O W O Ph O W O Ph O W O
O O O O R O O R
R R

R H – (CH2)5Me

N N

max (nm) 407 420 402 396 427

τ (s) 4.6 74.9 83.6 42 62
E0,0 (eV) 2.39 2.70 2.59 2.22 2.36
Ered (V vs. SCE) –1.29 –1.24 –1.34 –1.42d –1.37d
Eox (V vs. SCE) +1.10 +1.41 +1.64 +1.55d +1.47d
red
*E (V vs. SCE) +1.10 +1.46 +1.25 +0.80 +0.99
*Eox (V vs. SCE) –1.29 –1.29 –0.95 –0.67 –0.89
Refs. 179,180 179 179,180 181 181

CO2Me 3+ 3+ Ph 3+
3+
CO2Me N
N
MeO2C CO2Me N N Ph Ph
N N N N
Cr Cr
N N N N
N N N N
Cr Cr
N N
N N N N
CO2Me
N N
MeO2C CO2Me Ph Ph

CO2Me Ph

max (nm) 480 480 454 484

τ (s) 7.7 87 304 425
E0,0 (eV) 1.70 1.70 1.70 1.67
Ered (V vs. SCE) +0.14 –0.02 –0.25 –0.27
ox
E (V vs. SCE) n/a n/a n/a n/a
*Ered (V vs. SCE) +1.84 +1.68 +1.45 +1.40
*Eox (V vs. SCE) n/a n/a n/a n/a
Refs. 182,183 182,183 182,183 182,183
a
Biexponential.
b
Redox potentials were originally referenced vs. Fc+/Fc in THF and are corrected by adding 0.56 V for referencing against the SCE.
c
Redox potentials were originally referenced vs. Fc+/Fc in CH2Cl2 and are corrected by adding 0.46 V for referencing against the SCE.
d
Redox potentials were originally referenced vs. Fc+/Fc in MeCN and are corrected by adding 0.40 V for referencing against the SCE.

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Table 7 Summary of Photophysical and Electrochemical Properties of Au Photosensitizers

OMe Ph 2+ 2+ R 2+
+ Ph R
P P P P P P
Ph Ph R R
Au Au Au Au Au Au
Ph Ph R R
P P P P P P
Ph Ph R R
CF3
N

Au R=

N N CF3

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max (nm) 403 320 n/a n/a
τ (s) 506 0.85 0.40 10000
E0,0 (eV) 2.48 2.23 2.36 2.10
Ered (V vs. SCE) –1.33a –1.63 –1.77 –1.65
Eox (V vs. SCE) n/a +0.70 +0.49 +1.41
red
*E (V vs. SCE) +1.15 +0.60 +0.59 +0.45
*Eox (V vs. SCE) n/a –1.53 –1.87 –0.69
Refs. 184 185–187 185 185

3+ 2+
Ph Ph
N N N N
Ph Ph P Ph Ph Me Me
Au Au Au Au Au
Ph Ph Ph Ph
P
Ph Ph Me N N N N Me

max (nm) n/a n/a

τ (s) 1500 0.02
E0,0 (eV) 2.28 2.44
red
E (V vs. SCE) –1.54 n/a
Eox (V vs. SCE) +1.09 +0.34
*Ered (V vs. SCE) +0.74 n/a
ox
*E (V vs. SCE) –1.19 –2.10
Refs. 185 185
a +
Redox potentials were originally referenced vs. Fc /Fc in MeCN and are corrected by adding 0.40 V for referencing against the SCE.

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Table 8 Summary of Photophysical and Electrochemical Properties of Pt Photosensitizers

F MeO OCH3 OCH3

+ +
N F
Pt N N
O O Pt Pt

O O O O N

N N
N Pt N
Pt Ph
P Ph
Ph P
Ph

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max (nm) 386 380 420 400–500 300–450
τ (s) 2.21 0.382 11.6 0.309 0.093
E0,0 (eV) 2.64 2.73 2.45 2.48 2.51
Ered (V vs. SCE) –2.38 –2.46 –2.20 –1.18a –1.29b
Eox (V vs. SCE) +0.57 +0.62 +0.52 n/a +1.01b
red
*E (V vs. SCE) +0.26 +0.27 +0.25 +1.30 +1.22
*Eox (V vs. SCE) –2.07 –2.11 –1.93 n/a –1.50
Refs. 188 188 188 189 190
a
The reference potential was not specified by the authors.
b
Redox potentials were originally referenced vs. Fc+/Fc in MeCN and are corrected by adding 0.40 V for referencing against the SCE.

Table 9 Summary of Photophysical and Electrochemical Properties of Ce Photosensitizers

SiMe3 iPr iPr Cy

Ce N N N N(SiMe3)2 N N(SiMe3)2
SiMe3 3 (Me3Si)2N Ce (Me3Si)2N Ce (Me3Si)2N Ce
N 3 N N(SiMe3)2 N N(SiMe3)2
iPr iPr Cy

max (nm) 415 424 423 423

τ (s) 0.024 0.0828 0.067 0.061
E0,0 (eV) 2.24 2.70 2.39 2.37
E red
(V vs. SCE) n/a n/a n/a n/a
Eox (V vs. SCE) +0.61a +0.24b +0.49b +0.59b
*Ered (V vs. SCE) n/a n/a n/a n/a
*E (V vs. SCE)
ox
–1.63 –2.46 –1.90 –1.78
Refs. 191–193 193 191–193 191,192

iPr Cl 3–
N R1 Cl Cl
(Me3Si)2N Ce N Ce
N 2 R2 Cl Cl
iPr Cl

R R1 = R2 = SiMe3 R1 = SiMe3; R2 = t-Bu R1 = SiMe3; R2 = i-Pr R1 = Ph; R2 = i-Pr R1 = R2 = Ph –

max (nm) 429 438 463 461 463 329
τ (s) 0.117 0.221 0.158 0.041 0.043 0.0221

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E0,0 (eV) 2.46 2.34 2.19 2.33 2.34 3.48

red
E (V vs. SCE) n/a n/a n/a n/a n/a n/a
Eox (V vs. SCE) +0.32b +0.20b +0.05b –0.11b –0.10b +0.43c
*Ered (V vs. SCE) n/a n/a n/a n/a n/a n/a
*Eox (V vs. SCE) –2.14 –2.14 –2.14 –2.44 –2.44 –3.05
Refs. 193,194 194 194 194 194 195,196
a +
Redox potentials were originally referenced vs. Fc /Fc in THF and are corrected by adding 0.56 V for referencing against the SCE.
b
Redox potentials were originally referenced vs. Fc+/Fc in CH2Cl2 and are corrected by adding 0.46 V for referencing against the SCE.
c
Redox potentials were originally referenced vs. Fc+/Fc in MeCN and are corrected by adding 0.40 V for referencing against the SCE.

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