Recent Advances in Metal-Based Molecular Photosensitizers for Artificial Photosynthesis

: Artificial photosynthesis (AP) has been extensively applied in energy conversion and environment pollutants treatment. Considering the urgent demand for clean energy for human society, many researchers have endeavored to develop materials for AP. Among the materials for AP, photosensitizers play a critical role in light absorption and charge separation. Due to the fact of their excellent tunability and performance, metal-based complexes stand out from many photocatalysis photosensitizers. In this review, the evaluation parameters for photosensitizers are first summarized and then the recent developments in molecular photosensitizers based on transition metal complexes are presented. The photosensitizers in this review are divided into two categories: noble-metal-based and noble-metal-free complexes. The subcategories for each type of photosensitizer in this review are organized by element, focusing first on ruthenium, iridium, and rhenium and then on manganese, iron, and copper. Various examples of recently developed photosensitizers are also presented.


Introduction
Over the past several decades, a large amount of fossil fuels have been exploited, especially during the Industrial Revolution [1][2][3].The overexploitation of fossil fuels not only destroys the environment but has also led to serious global climate change and an energy crisis, which directly threaten the survival of humanity.To resolve these problems, thousands of green power sources are in development [4][5][6].The Sun provides much more energy than current global demand; hence, it has become desirable in the development of novel sustainable energy.Artificial photosynthesis (AP), such as photocatalytic water splitting or CO2 reduction, can achieve the conversion of solar energy into chemical fuels, including carbon-free hydrogen as an environmentally friendly fuel, and industrial raw materials such as methanol [7][8][9][10].Among various photosynthetic systems, molecularbased multi-component systems have been a research hotspot because of their properties, which can be controlled by the reasonable design of their chemical structures [11][12][13].In a multi-component system, a photosensitizer plays an important role in light absorption and electron transfer; therefore, intense research has been devoted to photosensitizers, particularly from 2012 to 2022 as shown in Figure 1.This booming exploration of metalcomplex-based photosensitizers has resulted in improving their performance and availability for commercial applications.

Photosynthesis in Nature
Natural photosynthesis in green plants and cyanobacteria is a critical reaction for the utilization of sunlight, which is crucial for providing sustainable energy on Earth.Photosynthesis in nature occurs through two unique photosystems, i.e., PSI and PSII, involving several electron transfer (ET) procedures [14].As shown in Figure 2a, PSII is triggered by the photoexcitation of P680 and the release of electrons to give P680 + , which is then involved in an oxygen-evolving reaction (OER).Simultaneously, PSI is initiated by the photoexcitation of P700, which then accepts electrons from the ET chain of PSII, resulting in the activation of the Calvin cycle, where CO2 is reduced into carbohydrates.

The Role of Photosensitizers in Artificial Photosynthesis
Inspired by nature, artificial photosynthesis (AP) simulates the function of critical components in a photocatalytic reaction [15].Unlike natural photosynthesis, AP can not only convert CO2 into biomass, but it can also produce various chemical fuels such as hydrogen.There are three processes in a multi-component artificial photosynthesis reaction: (i) the light harvesting process in which a photosensitizer absorbs sunlight efficiently and then is converted into an excited state (PS * ); (ii) the charge generation and separation step in which electron-transfer occurs between the PS * and an e -acceptor/donor; (iii) a catalytic reaction.Clearly, a photosensitizer plays an important role in the absorption of solar photons and the injection of the photoexcited electrons into an acceptor in a photocatalytic reaction.

A General Scheme for Photosensitizer-Involved Photocatalysis
Figure 2b illustrates a general scheme for a photosensitizer-involved AP reaction.A ground-state photosensitizer (PS) is excited by sunlight and form PS * via a metal-to-ligand charge transfer (MLCT), i.e., electron-transfer occurs between the metal orbital and ligand orbital.PS * then undergoes electron transfer quenching (reductive or oxidative) in the presence of a donor or an acceptor, i.e., sacrificial agent (SA) resulting in the formation of a reduced photosensitizer (PS − ) or oxidized photosensitizer (PS + ).Finally, PS − or PS + can be re-oxidized or be re-reduced back to PS in a catalytic reaction for CO2 reduction, hydrogen generation, or water oxidation [16][17][18].However, it is worth noting that there are two competing side reactions that take place: (i) the PS * decays to PS by heat or a nonradiative pathway; (ii) back electron transfer occurs between SA -and PS + or between SA + and PS − .Therefore, to improve the overall photocatalytic efficiency, the lifetime of an excited state PS * must be long enough to overcome these side reactions.Meanwhile, it requires that PS − or PS + provides a suitable driving force to make catalysis occurs.In addition, because solar irradiation (AM1.5G)consists of only ~4% ultraviolet light (λ < 400 nm) and ~43% near-infrared light (λ > 800 nm) but also ~53% visible light (400 nm < λ < 800 nm), the ground-state PS should absorb as much visible light as possible to obtain a strong amount of energy from sunlight [19].
Due to the crucial role of photosensitizer(s) in AP, a comprehensive review on photosensitizers for solar hydrogen generation was published in 2017 [20].In this review, some criteria of evaluating molecular photosensitizers were first described, and then recent achievements on metal-based photosensitizers and their importance in artificial photosynthesis were summarized and highlighted.The photosensitizers were categorized into two main families: noble-metal and noble-metal-free complexes.Noble-metal photosensitizers include ruthenium-, iridium-, and rhenium-based complexes, while noblemetal-free photosensitizers contain manganese-, iron-, copper-, and other metal-based complexes.

Parameters for Evaluating Photosensitizers
Some desirable characteristics for a photosensitizer include: (i) strong absorption of a distinguished range of the solar spectrum; (ii) a long excited-state lifetime (ns~µs); (iii) chemical stability in solution; (iv) reversible redox potentials.Therefore, several parameters are derived to evaluate the performance of photosensitizers.

UV-Vis Absorption
In metal coordinating complexes, intense absorptions may arise from the transfer of electronic charges between ligand orbitals and metal orbitals, either ligand-to-metal charge transfer (LMCT) or metal-to-ligand charge transfer (MLCT).Since ligands for MLCT usually have vacant, low-lying π * orbitals, such as py, bpy, phen, and other aromatic ligands, which are widely used in molecular metal photosensitizers, MLCT has been discussed in previous studies more often than LMCT in photocatalytic processes; hence, herein, MLCT was the focus.As mentioned previously, charge transfer transition is a critical process in artificial photosynthesis.For effective utilization of solar light, a basic requirement for a photosensitizer is absorbing sunlight over the visible wavelength and initiating electron transfer from or to its excited state.Using the description above, measuring UV-Vis absorption is usually the first and one of the most important steps in estimating the photocatalytic applications of a photosensitizer.
There are two main parameters that can be obtained by the UV-Vis spectrum: (i) The charge transfer wavelength λ (in nm): (ii) The molar extinction coefficient (or absorption), which is independent of concentration, and calculated by: where Amax is the maximum absorbance; c is measured in mol dm −3 , and the cell path length, l, is in cm.

Ground-State Redox Potential
The ground-state redox properties of photosensitizers are important indicators for photocatalysis.A common method of measuring ground-state redox potentials for metal complexes is cyclic voltammetry (CV).Generally, CV can reflect the oxidation of the metal center and the reduction of ligands in a complex.Take the [M(L1)(L2)] n complex, owing to its MLCT character, as an example [21].The electron transfer processes are: (i) Oxidation: (ii) Reductions: In addition to the oxidation and reduction abilities, the stability of a photosensitizer is another important consideration, since it must be capable of being regenerated over multiple turnovers in a photosynthesis reaction.As a result, the reversibility of the above redox processes, being demonstrated by cyclic voltammetry, is also important.
Since MLCT transition is accompanied by the occurrence of metal oxidation and ligand reduction, a correlation between the energies of the charge transfer absorptions and the electrochemical properties is established without considering the solvation and electron correlation effects: Evidently, the electrochemical data deconvolve important details, but the value of E MLCT alone is insufficient to determine whether a photosensitizer is suitable for a photocatalysis reaction.

Steady-State Emission
For a typical metal-based photosensitizer, the radiative quantum yield (Φ) can be calculated from the ratio between the number of emitted photons and the number of absorbed photons: where Iem can be obtained from the steady-state emission spectrum.According to Lakowicz's method in Principles of Fluorescence Spectroscopy [22], the relative quantum yield can be calculated using Equation (9): where Int is the area under the emission peak; A is the absorbance at the excitation wavelength; η is the refractive index of the solvent.For the same type of photosensitizers in the same solvent, the absorbance value A is similar and η is the same, and the above equation can be simplified as Equation (10):

Excited-State Redox Potential
For a multi-component photocatalytic process, the driving force of a photosensitizer must be adequate.As a result, the value of E([M] n + 1 / * [M] n ), which reflects the electrondonating ability, must be more negative than the reduction potential of the catalyst so that electron(s) can be transferred from the excited state to the catalyst.Conversely, the value of E([M] n / * [M] n − 1 ), which reflects the electron-accepting ability, must be more positive than the reduction potential of the catalyst (usually in a high oxidation state) to ensure the electron transfer occurs to the excited state.In this way, the excited-state redox potentials for molecular photosensitizers are calculated by the following equations: (i) Oxidative quenching: (ii) Reductive quenching: where ) are the ground-state potentials.E 0 can be estimated from one of the following methods: (i) the crossover point of the lowest-energy MLCT absorption band and the corresponding emission band [23]; (ii) the crossover point of the tangent line of the emission spectrum (left half) with a wavelength axis [24]; (iii) the first vibronic band in the low-temperature emission spectrum [25] (see details below).
Clearly, the excited-state redox potential is an important indicator for evaluating photosensitizers, but it should be noted that the calculation of the excited-state redox potential may have some error because of the uncertainty of E0.

Lifetime
To simplify our discussion, two states for a photosensitizer after being excited are shown in Figure 3: the singlet state 1 MLCT (S1) and the triplet state 3 MLCT (T1).The S1 state can decay to the ground state (S0) via a radiative way, i.e., fluorescence (kr) and/or a nonradiative way (knr).Afterwards, the singlet-triplet transition happens through intersystem crossing (ISC) with the association of energy loss as heat (kISC).Thereafter, the T1 state's decay to the S0 state follows a similar way as the S1 state: a radiative way, i.e., phosphorescence (k r ' ) and/or a nonradiative way (k nr ' ).Therefore, these decay constants (hence, lifetime) are important criteria for evaluating a photosensitizer.Generally, the lifetime (τ 0 ) of a photosensitizer is measured by excited-state transient absorption (TA) spectra and the signal fit to single [24] or triple [26] (depends on the mechanism of photosensitizers) exponential decay kinetics.To complete a photocatalytic reaction, the excited-state lifetime must be long enough to overcome the decay process. where Through measuring τ 0 , k r can be calculated by Equation ( 16): Therefore, knr can be calculated by combining Equations ( 9), ( 15) and ( 16) as shown below:

Marcus Electron-Transfer Theory
Since photocatalytic reactions are essentially electron transfer (ET) processes, the kinetics of ET is governed by Marcus theory, shown in Equation (18).
where   refers to the Boltzmann constant; T is the temperature (K); h refers to Planck's constant; λ refers to the reorganization energy.ΔG0 is the driving force of the electrontransfer reaction as shown below: Apparently, increasing the driving force can improve the rate of electron transfer, i.e., the rate of catalysis as indicated by the excited-state potential equations and the Marcus relationship [27].However, Marcus theory also demonstrates that there is a Marcus inverted region, where a stronger driving force leads to slower ET rates, hence, there is no normal standard criterion for photosensitizers for all photocatalytic reactions.

Stern-Volmer Quenching
Because of the occurrence of back-electron transfer between photosensitizers and catalysts, it is necessary to add a sacrificial reagent to most photocatalytic reactions.K SV is calculated from the emission quenching data as a function of the concentration of persulfate, which follows the Stern-Volmer relationship: where Using above discussions, the radiative quantum yield of a photosensitizer shows a dependent relationship with the concentration of a quencher, i.e., [Q]:

Turnover Frequency (TOF)
TOF is an essential parameter of a catalyst, reflecting its catalytic activity and performance.A recent review by Xiujuan Wu and Licheng Sun outlined several calculation methods for evaluating catalysts [28].It is less common to calculate the TOF for a photosensitizer than for a catalyst but, in some cases, when a standard catalyst is applied, TOF becomes an important criterion for comparing the performances of different photosensitizers.From the perspective of a definition, TOF refers to the amount of product converted from the reactant per mol of the effective photosensitizer per unit time.

TON =
amount of transfered electrons for product(moles) amount of photosensitizer (moles) TOF = TON time of reaction (25) Since the plot of TON versus time does not usually follow a linear relationship, the TOF is taken from the pseudo-first-order rate constant, i.e., the maximum photocatalytic rate.

Ru-Based Photosensitizers
The ruthenium-polypyridine family is an early-developed photosensitizer [38], and its fundamental properties and mechanisms have been well investigated [39][40][41][42][43]. Current research efforts on this family of photosensitizer focus on improving its photochemical stability, antidecomposition, extreme pH value tolerance, and driving force at various environmental conditions.
Concepcion et al. developed a series of homoleptic Ru(II) polypyridyl complexes (Figure 4a), which showed decent photochemical water oxidation performance at pH 1 [24].By modifying electron-withdrawing groups (i.e., −CF3 and −PO3H2) at the 4, 4', or 5' positions of bpy ligands, the redox potentials increased to as high as 1.6 V (vs.NHE) at pH 1.It is worth mentioning that unlike heteroleptic complexes, the redox potentials of which can be increased at the expense of decreasing the excited-state lifetimes [44], some of these homoleptic Ru(II) polypyridyl complexes presented increased lifetimes from 580 to 731 ns at pH 1. Their studies illustrated that replacing H with electron-withdrawing groups in homoleptic complexes provides a feasible strategy for designing and synthesizing high-performing photosensitizers at pH 1.The kinetic isotope effects (KIEs) of the PO3H2-containing complexes proved the concerted EPT between the photosensitizer and catalyst for the first time.In addition to [Ru(bpy)3] 2+ -type photosensitizers, [Ru(phen)3] 2+ complexes are another family of Ru photosensitizers, but they are more used in CO2 reduction reactions (CO2RR).However, the excited-state lifetime of raw [Ru(phen)3] 2+ complexes is short (360 ns in CH3CN), resulting in a weakened photocatalytic performance for CO2RR.It has been proved that adding a conjugated group can improve the excited-state lifetime, but an improper introduction will make the excited oxidation potentials worse.To address this problem, Lu et al. creatively synthesized pyrene-modified [Ru(phen)2(L)] 2+ photosensitizers (Figure 4b) and realized the fine-tuning of PS properties for efficient CO2 reduction.The conjugated group, pyrene, greatly improved the sensitizing ability of [Ru(phen)3] 2+ complexes.Especially, [Ru(phen)2(3-pyrenylphen)] 2+ (Ru-3) showed a moderate excitedstate lifetime (68.2 µs) but a 17 times larger TOF than [Ru(phen)3] 2+ with a large TON of 66,480 [45].Their study clearly illustrated the importance of balancing lifetime and potential in improving the overall performance of photocatalytic systems.

Ru
In recent years, multielectron accumulation has been considered an effective strategy for improving photocatalytic performance.Several studies have shown that naphthalene [46], anthraquinone [47], and dipyrido-[3,2-a:2',3'-c]phenazine (dppz) [48] own the electron-storage ability and can enhance the efficiency of light-driven processes.These bentbridging-ligands involve ruthenium complexes; however, they usually require ingenious design of molecular structures and smart synthesis procedures for ligands.On the foundation of dppz-based complexes, Dietzek and Kerlidou et al. modified a pyridoquinolinone subunit on dppz (Figure 4c) [49] aimed at realizing electron accumulation by extending the π system.Various methods proved the 2e − /2H + mechanism of this photosensitizer and demonstrated its potential applications in producing H2O2.

Ir-Based Photosensitizers
Although Ru-based photosensitizers have shown vast potential in solar energy conversion, their poor photostability limit their application.In responding to this problem, Ir (III) complexes have drawn particular attention in replacing Ru (II) complexes over the past decade.In 2018, Bernhard et al. thoroughly reviewed Ir (III)-type photosensitizers [50]; hence, this review focused only on the development of Ir photosensitizers thereafter.
[Ir(ppy)2(bpy)] + and its derivatives (Figure 5a) have been extensively studied as photosensitizers for energy conversion due to the fact of their decent photostability.Based on these studies, in 2020, Dietzek et al. developed and studied a series of iridium complexpolyoxometalate (POM) dyads, Ir-POMM, which have shown high efficiency in photocatalytic hydrogen evolution reactions [51,52].By changing the central metal of POM from Mn 3+ to Fe 3+ to Co 3+ , the yields of charge-separated state Ir + -POMM − (i.e., the rate-limiting intermediate) decreased, while the lifetime increased from 290 to 540 ps.A photoinduced electron transfer dynamics study illustrated that the catalytic capacity decreased in the order Ir-POMMn > Ir-POMCo > Ir-POMFe, which was in the same order of the yields of Ir + -POMM − , demonstrating the high impact of yield on the catalytic capacity.In 2021, Teets et al. prepared a series of β-diketiminate-modified (NacNac) iridium complexes as demonstrated in Figure 5b.The electron-rich NacNac ligands dramatically improved the photoinduced electron transfer rate, as indicated by the decreased excited redox potential from −2.1 to −2.5 V (vs.Fc + /Fc), making various challenging photoredox reactions occur under moderate conditions with high yield [53,54].Later, they further improved the photocatalytic performance by replacing ppy with ptz and pmb, all of which presented significant excited redox potentials in the range of −2.4 to −2.8 V [55].Their studies put forward practical proposals for designing novel photosensitizers with high efficiency and feasible photostability.

Re-Based Photosensitizers
Rhenium photosensitizers are usually found in the family of [Re(bpy)(CO)3Cl] complexes.Ishitani et al. developed a series of highly efficient rhenium(I) trinuclear photosensitizers (Figure 6a) for photocatalytic CO2 reduction [56].As a consequence of the efficient reductive quenching of the Re-ring by triethanolamine and fast electron transfer, the CO2 reduction process showed high photocatalytic efficiencies.A summary of the characteristics and properties of Re(I) diimine complexes weree published by Ishitani et al. in 2017 [57].In 2020, by modifying the [Re(bpy)(CO)3Cl] complex with an anchoring group, -PO3H2 (Figure 6b), Hamm et al. successfully loaded it with a cobalt catalyst, [Co(DMTPy-O-benzyl-3,5-bis(MePO3H)], on ZrO2, demonstrating the possibility of constructing heterogeneous photocatalytic systems using Re photosensitizers [58].Recently, Fernandez-Tera ́ n et al. reported the feasibility of tuning the properties of rhenium(I) tricarbonyl complexes through changing the substituent with various groups (i.e., CN, CF3, Br, H, OMe, and NMe2) as shown in Figure 6c.It was found that the complex with the most electron-donating group, NMe2, showed a notable lifetime of 380 ns and a TON of over 2100 [59].This is the first example of applying the 3 ILCT state of a rhenium(I) tricarbonyl complex as a stable photosensitizer.
These studies implied that Re-based complexes are good candidates for replacing ruthenium as photosensitizers for stable photocatalytic reactions.
Table 1 summarized the properties of noble-metal-based photosensitizers in this review, as shown below.

Noble-Metal-Free Photosensitizers
Over the last decade, the investigation of photosensitizers based on nonprecious transition metals dramatically increased owing to their favorable (photo)physical properties, high earth abundancy, and low cost.Table 2 shows the earth abundancy of the metal elements mentioned in this review.However, due to the fact of these photosensitizers' feature of unwanted nonradiative decay, they generally perform worse than noble-metalbased photosensitizers in terms of photophysical properties (i.e., MLCT and lifetime) and redox potential [60].Nevertheless, nonprecious transition metal complexes have shown highly attractive potentials in photocatalytic hydrogen production and CO2 reduction [61].In the subsequent sections, recent advances in noble-metal-free photosensitizers from low atomic number to high atomic number are summarized.

Mn-Based Photosensitizers
Manganese plays an essential role in absorbing light in natural photosynthesis process; hence, it has inspired the development of Mn-based nanomaterials for photocatalysis [63][64][65][66].However, due to the fact of their intrinsic nonradiative decay of excited states, it is still a grand challenge to make Mn-based complexes luminescent and photoactive.
Wenger et al. recently reported a family of novel isocyanide Mn(I) complexes, [Mn(L bi )3] + and [Mn(L tri )2] + , that exhibited the first example of manganese complexes with luminescent MLCT and photo-reactivity at room temperature [67,68] as shown in Figure 7.This series of Mn-based homoleptic photosensitizers is air-stable and nontoxic, and the redox potential of Mn(I/II) is reversible.Spectrum studies gave a 1 MLCT absorption wavelength at ~390 nm and an emission wavelength at ~500 nm.These complexes have been successfully applied in energy conversion reactions.Unlike traditional energy transfer pathways (i.e., MLCT, LMCT, and MC excited states), their study provide the attractive possibility of realizing the triplet-energy-transfer photo-reactivity by a ligand-centered ππ * state.Currently developed Mn-based complexes are not comparable with traditional noble-metal-based photosensitizers in terms of excited-state lifetime or driving force for photocatalytic reactions, but these studies open new avenues to exploring cheap bio-inspired molecules for artificial photosynthesis.
Kunnus et al. recently reported a series of [Fe(N^N)(CN)4] 2--type photosensitizers, where N^N represents 2,2'-bipyridine (bpy); 2,3-bis(2-pyridyl)pyrazine (bpyz); 2,2'-bipyrimidine (bpym), respectively (Figure 8a), and studied the solvent effect on the chemical properties as well as the MLCT excitation energy dependence of the 3 MLCT lifetime.Femtosecond transient absorption (TA) data and td-DFT calculations revealed the tunability of the excited-state relaxation mechanisms and charge transfer lifetimes, which increased from 0.22 to 16.9 ps with an increasing number of nitrogen in the ligand.In addition to iron(II) polypyridyl complexes, iron (II) N-heterocyclic carbene (NHC) complexes (Figure 8b) have been extensively investigated as photosensitizers [75][76][77][78][79].The strong bonding between ion and the carbene ligands leads to increased ligand-field splitting, resulting in the destabilization of the MC states.As a consequence, Fe(II)-NHC-type photosensitizers present prominent properties such as long excited-state lifetimes and high charge transfer abilities [77].Bauer et al. studied the relationships between the number of NHC ligands and the photophysical properties of Fe photosensitizers.An increasing trend in the 3 MLCT lifetime was found when there was an increase in the number of NHC ligands [78].In their follow-up study, the excited-state dynamics of [Fe II (tpy)(pyz-NHC)] 2+ was investigated.The results of intersystem crossing and triplet dynamics further interpreted the excellent performance of Fe(II)-NHC photosensitizers.
At present, the photophysical properties and stability of Fe-based photosensitizers are not comparable to Ru-based complexes.However, its high earth-abundancy and low cost attract continuous attention.Future work on Fe-based photosensitizers will focus on extending their charge-separated state and improving their photostability.

Cu-Based Photosensitizers
Copper-based photosensitizers have been popular since the 1970s because of their MLCT nature and high earth abundancy [80][81][82][83][84].With the extensive study of copper complexes, Cu-based photosensitizers possessing considerable properties and good performances have increasingly been developed.Unlike other abundant transition metals, copper complexes have a filled d subshell, which blocks the formation of a metal-centered excited state.Therefore, many copper (I) complexes show MLCT luminescence [60].As a result of its sustainability and photophysical properties, in recent years, copper is replacing ruthenium for use as molecular photosensitizers in dye-sensitized solar cells (DSSCs) [85].Housecroft and Constable have reviewed the progress of copper(I)-containing DSSCs [86].
Mulfort et al. developed and studied a series of copper(I) diimine photosensitizers based on the HETPHEN method [87,88] and immobilized these photosensitizers on the metal oxide surface via carboxylate groups [26].The CuHETPHEN strategy provides many more possibilities for tuning the structures and properties of copper photosensitizers.These discoveries related to copper complexes promote important improvements in Cu-based photosensitizers and further increase their potential applications in the solar energy conversion industry.The photochemical processes of copper-based photosensitizers have been well explored by advanced technologies such as spectroscopics [89][90][91][92].In general, ground-state copper complex is excited into a singlet MLCT state, which then undergoes a flattening distortion and becomes triplet MLCT state.Depending on the coordination ability of the solvent, the 3 MLCT state complex may or may not bind the solvent molecule.After experiencing a strong interacting, the complex recovers to the ground state as shown in Figure 9. Chen et al. reviewed the photocatalytic mechanisms of copper(I) diimine complexes and their developments and applications in solar energy conversion in 2015 [93].From a chelating element perspective, there are four types of copper (I) photosensitizers: Cu(N^N)(N^N), Cu(N^N)(P^P), Cu(N^N)(N^P), and Cu(N^P)(N^P) as shown in Figure 10a.In terms of Cu(N^N)(N^N)-type photosensitizers, Hadt et al. quantified the entatic effects of several [Cu(phen-X)2] + complexes, where X are the 2,9-alkyl substitutions, and correlations were found between the lifetime, the excited-state relaxation energy, the reorganization energy, and the energy gap [94].Castellano et al. successfully prepared various Cu-phen MLCT photosensitizers featuring bulky substituents.Impressive photophysical properties (τ = 1.5 μs, Φ = 2.6% in acetonitrile) were discovered when use dchtmp as the ligand.Their C−C radical coupling photochemistry strategy broke through the traditional limit of steric bulk possibility for homoleptic Cu(I) complexes [95,96].In recent years, scientists have aimed at replacing nitrogen with phosphines in transition-metal-based photosensitizers.Generally, the introduction of phosphines usually brings about a higher stability and lower redox potentials [97][98][99][100][101][102].Karnahl et al. prepared a hetero-bidentate P^N ligand, phox, and improved the performance of Cu-based + photosensitizers, the influences of expending π-systems were discovered [103].Dietzek et al. [91] and Karnahl et al. [104] recently studied the extended π-system effect on the properties of [Cu(xant)(dppz)] + and [Cu(xant)(dmdppz)] + .The extended π-system provided unusual properties such as broadening and a red-shift of the MLCT absorption and a prolonged lifetime.Dietzek et al., in particular, studied the effect of the electronic structures of Cu(I) photosensitizers containing phosphines [105].Their study on the Franck−Condon region of heteroleptic Cu(I) complexes provides new theoretical principles for designing Cu-based photosensitizers.Bruggeller et al. recently reviewed the development of photosensitizers with phosphines and summarized the influence of phosphines on the properties of photosensitizers [106].
Among the aforementioned noble-metal-free complexes, the copper family has the greatest potential to replace noble-metal photosensitizers as indicated by their promising photophysical properties such as long lifetimes.Nevertheless, their poor chemical stability and environmental sensitivity (to pH value, humidity, etc.) impede their broad applications in energy conversion.Efforts towards improving these properties will be the focus of future research.

Other Photosensitizers
Other types of metal-based photosensitizers are less common than manganese, iron, and copper.Inspired by natural photosynthesis, many of these photosensitizers (Figure 11) are based on porphyrin and its derivatives, which itself is a biomimetic light-harvesting molecule [107][108][109].Poddutoori et al. reviewed unique aluminum (III) porphyrin complexes, which can act as either electron donor or electron acceptor in donor-acceptor systems because of their redox and optical properties [110].Park et al. creatively designed positively charged Zn and neutral Sn porphyrins complexes, [ZnTMePyP4 + ]Cl4 and Sn(OH)2TPyP, Sn(Cl2)TPP-[COOMe]4, and Sn(Cl2)TPP-[PO(OEt)2]4, as photosensitizers for H2 evolution.Their study clearly demonstrated the influence of pH value as well as solution concentration.It also showed that the photocatalytic process can be realized by oxidative quenching of the photosensitizer [111].The results of this study shed light on designing and synthesizing metal-containing photosensitizers based on porphyrin.Willner et al. developed an all-DNA system with Zn (II)-protoporphyrin IX (Zn II PPIX) as a photosensitizer [112].In this mimic PSI system, Zn II PPIX presented effective photoinduced electron transfer (ET).Their report provides a versatile approach for designing supramolecular photosensitizers.Detailed parameters for some of above noble-metal-free photosensitizers are summarized in Table 3.  () .c Potential versus Fc +/0 standard in CH3CN.d Potential versus Fc +/0 standard in DMF.

Conclusions and Outlook
This review endeavored to summarize the evaluating parameters and recent work on metal-based molecular photosensitizers.Noble-metal-based photosensitizers, such as ruthenium, iridium, and rhenium, are the most investigated metal-based photosensitizers and many reviews on these photosensitizers are available; hence, here, recent advances in noble-metal-based photosensitizers were briefly reviewed.These photosensitizers, however, are scarce, expensive, and toxic to humans.Thus, noble-metal-free photosensitizers have become research hotspots in the solar energy conversion field.Due to the fact of their valuable photophysical properties and their charge-separation ability to induce photochemistry, manganese, iron, and copper, they have recently received particular attention.Some photosensitizers were found to be active, but further work in promoting their higher efficiency and stronger stability as well as a greater understanding of their mechanisms are needed for their large-scale industrial application.In addition to the metal-based photosensitizers that were highlighted in this review, biomolecular photosensitizers, such as from natural bacterial sources, are another attractive alternative to expensive metal-based photosensitizers.
Funding: This research received no external funding.

Figure 2 .
Figure 2. (a) The Z-scheme coupling PSI and PSII in natural photosynthesis; (b) the general scheme of the quenching pathway in photocatalytic reactions.PS: photosensitizer; A: electron acceptor; D: electron donor; Cat: catalyst.

Figure 10 .
Figure 10.Chemical structures of the (a) Cu-based photosensitizers and (b) corresponding ligands in this review.
photosensitizers[100].Ishitani et al. synthesized [Cu(dmp)(DPEphos)] + complexes, where DPEphos is 2-(diphenylphosphino)phenyl]ether, for photocatalytic CO2 reduction.By comparing the properties of a series of [Cu(N^N)(DPEphos)] + photosensitizers, the influences of expending π-systems were discovered[103].Dietzek et al.[91] and Karnahl et al.[104] recently studied the extended π-system effect on the properties of [Cu(xant)(dppz)] + and [Cu(xant)(dmdppz)] + .The extended π-system provided unusual properties such as broadening and a red-shift of the MLCT absorption and a prolonged lifetime.Dietzek et al., in particular, studied the effect of the electronic structures of Cu(I) photosensitizers containing phosphines[105].Their study on the Franck−Condon region of heteroleptic Cu(I) complexes provides new theoretical principles for designing Cu-based photosensitizers.Bruggeller et al. recently reviewed the development of photosensitizers with phosphines and summarized the influence of phosphines on the properties of photosensitizers[106].Among the aforementioned noble-metal-free complexes, the copper family has the greatest potential to replace noble-metal photosensitizers as indicated by their promising photophysical properties such as long lifetimes.Nevertheless, their poor chemical stability and environmental sensitivity (to pH value, humidity, etc.) impede their broad applications in energy conversion.Efforts towards improving these properties will be the focus of future research.

Table 1 .
Summary of the properties of the partial noble-metal-based photosensitizers in this review.

Table 3 .
Summary of the properties of the partial noble-metal-free photosensitizers in this review.
a Data obtained in dichloromethane at 20 °C, potential versus SCE in CH3CN.b Data were calculated from 1240