Bimolecular Excited-State Proton-Coupled Electron Transfer within Encounter Complexes.

Bimolecular excited-state proton-coupled electron transfer (PCET*) was observed for reaction of the triplet MLCT state of [(dpab)2Ru(4,4'-dhbpy)]2+ (dpab = 4,4'-di(n-propyl)amido-2,2'-bipyridine, 4,4'-dhbpy = 4,4'-dihydroxy-2,2'-bipyridine) with N-methyl-4,4'-bipyridinium (MQ+) and N-benzyl-4,4'-bipyridinium (BMQ+) in dry acetonitrile solutions. The PCET* reaction products, the oxidized and deprotonated Ru complex, and the reduced protonated MQ+ can be distinguished from the excited state electron transfer (ET*) and the excited state proton transfer (PT*) products by the difference in the visible absorption spectrum of the species emerging from the encounter complex. The observed behavior differs from that of reaction of the MLCT state of [(bpy)2Ru(4,4'-dhbpy)]2+ (bpy = 2,2'-bipyridine) with MQ+, where initial ET* is followed by diffusion-limited proton transfer from the coordinated 4,4'-dhbpy to MQ0. The difference in observed behavior can be rationalized based on changes in the free energies of ET* and PT*. Substitution of bpy with dpab results in the ET* process becoming significantly more endergonic and the PT* reaction becoming somewhat less endergonic.

Heterotrimetallic Assemblies with 1,2,4,5-Tetrakis(diphenylphosphino)benzene Bridges: Constructs for Controlling the Separation and Spatial Orientation of Redox-Active Metallodithiolene Groups.

Metallodithiolene complexes of the type [(R2C2S2)M(η2-tpbz)] [R = CN, Ph, or p-anisyl; M = Ni2+, Pd2+, or Pt2+; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene] chelate transition metals ions to form trimetallic arrays [[(R2C2S2)M(tpbz)]2M']n+, where M' is square planar Pt2+, tetrahedral Cu+, Ag+, or Au+, or octahedral {ReBr(CO)}/{Re(CO)2}+. Forcing conditions (190 °C reflux in decalin, 72 h) are demanded for the Re+ compounds. With third-row metals at the nexus, the compounds are stable to air. Twelve members of the set have been characterized by X-ray diffraction and reveal dithiolene centroid-centroid distances ranging from 22.4 to 24.0 Å. Folding around each tpbz intrachelate P···P axis such that the MP2/M'P2 planes meet the tpbz P2C6P2 mean plane at non-zero values gives rise to core topologies that appear "S-like" or herringbone-like for M' = Pt2+ or {ReBr(CO)}/{Re(CO)2}+. Calculations reveal that departure from idealized D2h/D2d/C2v symmetries is induced by steric crowding between Ph groups and that dynamic, fluxional behavior is pertinent to the solution phase because multiple, lower-symmetry minima of comparable energy exist. Spectroscopically, the formation of the trimetallic arrays is marked by a shift of the open end 31P nuclear magnetic resonance signal from approximately -14.5 ppm to approximately +41, approximately +20.5, and approximately +28.5 ppm for M' = Pt2+, Au+, and {ReBr(CO)}/{Re(CO)2}+, respectively. Electrochemically, dithiolene-based oxidations are observed for the R = Ph and M' = Pt2+ or Au+ compounds but at potentials that are anodically shifted relative to charge-neutral [[(R2C2S2)M]2(µ-tpbz)]. The compounds reported clarify the possibilities for the synthesis of assemblies in which weakly coupled spins may be created in their modular (R2C2S2)M and M' parts.

Platinum@Hexaniobate Nanopeapods: A Directed Photocatalytic Architecture for Dye-Sensitized Semiconductor H2 Production under Visible Light Irradiation.

Platinum@hexaniobate nanopeapods (Pt@HNB NPPs) are a nanocomposite photocatalyst that was selectively engineered to increase the efficiency of hydrogen production from visible light photolysis. Pt@HNB NPPs consist of linear arrays of high surface area Pt nanocubes encapsulated within scrolled sheets of the semiconductor H x K4-x Nb6O17 and were synthesized in high yield via a facile one-pot microwave heating method that is fast, reproducible, and more easily scalable than multi-step approaches required by many other state-of-the-art catalysts. The Pt@HNB NPPs' unique 3D architecture enables physical separation of the Pt catalysts from competing surface reactions, promoting electron efficient delivery to the isolated reduction environment along directed charge transport pathways that kinetically prohibit recombination reactions. Pt@HNB NPPs' catalytic activity was assessed in direct comparison to representative state-of-the-art Pt/semiconductor nanocomposites (extPt-HNB NScs) and unsupported Pt nanocubes. Photolysis under similar conditions exhibited superior H2 production by the Pt@HNB NPPs, which exceeded other catalyst H2 yields (µmol) by a factor of 10. Turnover number and apparent quantum yield values showed similar dramatic increases over the other catalysts. Overall, the results clearly demonstrate that Pt@HNB NPPs represent a unique, intricate nanoarchitecture among state-of-the-art heterogeneous catalysts, offering obvious benefits as a new architectural pathway toward efficient, versatile, and scalable hydrogen energy production. Potential factors behind the Pt@HNB NPPs' superior performance are discussed below, as are the impacts of systematic variation of photolysis parameters and the use of a non-aqueous reductive quenching photosystem.

Photocatalytic H2-Evolution by Homogeneous Molybdenum Sulfide Clusters Supported by Dithiocarbamate Ligands.

Irradiation at 460 nm of [Mo3(µ3-S)(µ2-S2)3(S2CNR2)3]I ([2a]I, R = Me; [2b]I, R = Et; [2c]I, R = iBu; [2d]I, R = CH2C6H5) in a mixed aqueous-polar organic medium with [Ru(bipy)3]2+ as photosensitizer and Et3N as electron donor leads to H2 evolution. Maximum activity (300 turnovers, 3 h) is found with R = iBu in 1:9 H2O:MeCN; diminished activity is attributed to deterioration of [Ru(bipy)3]2+. Monitoring of the photolysis mixture by mass spectrometry suggests transformation of [Mo3(µ3-S)(µ2-S2)3(S2CNR2)3]+ to [Mo3(µ3-S)(µ2-S)3(S2CNR2)3]+ via extrusion of sulfur on a time scale of minutes without accumulation of the intermediate [Mo3S6(S2CNR2)3]+ or [Mo3S5(S2CNR2)3]+ species. Deliberate preparation of [Mo3S4(S2CNEt2)3]+ ([3]+) and treatment with Et2NCS21- yields [Mo3S4(S2CNEt2)4] (4), where the fourth dithiocarbamate ligand bridges one edge of the Mo3 triangle. Photolysis of 4 leads to H2 evolution but at ∼25% the level observed for [Mo3S7(S2CNEt2)3]+. Early time monitoring of the photolyses shows that [Mo3S4(S2CNEt2)4] evolves H2 immediately and at constant rate, while [Mo3S7(S2CNEt2)3]+ shows a distinctive incubation prior to a more rapid H2 evolution rate. This observation implies the operation of catalysts of different identity in the two cases. Photolysis solutions of [Mo3S7(S2CNiBu2)3]+ left undisturbed over 24 h deposit the asymmetric Mo6 cluster [(iBu2NCS2)3(µ2-S2)2(µ3-S)Mo3](µ3-S)(µ3-η2,η1-S',η1-S″-S2)[Mo3(µ2-S)3(µ3-S)(S2CNiBu2)2(µ2-S2CNiBu2)] in crystalline form, suggesting that species with this hexametallic composition and core topology are the probable H2-evolving catalysts in photolyses beginning with [Mo3S7(S2CNR2)3]+. When used as solvent, N,N-dimethylformamide (DMF) suppresses H2-evolution but to a greater degree for [Mo3S4(S2CNEt2)4] than for [Mo3S7(S2CNEt2)3]+. Recrystallization of [Mo3S4(S2CNEt2)4] from DMF affords [Mo3S4(S2CNEt2)4(η1,κO-DMF)] (5), implying that inhibition by DMF arises from competition for a Mo coordination site that is requisite for H2 evolution. Computational assessment of [Mo3S4(S2CNMe2)3]+ following addition of 2H+ and 2e- suggests a Mo(H)-µ2(SH) intermediate as the lowest energy species for H2 elimination. An analogous pathway may be available to the Mo6 cluster via dissociation of one end of the µ2-S2CNR2 ligand, a known hemilabile ligand type, in the [Mo3S4]4+ fragment.

Dodecaphenyltetracene.

Dodecaphenyltetracene (4), the largest perphenylacene yet prepared, was synthesized from known tetraphenylfuran, hexaphenylisobenzofuran, and 1,2,4,5-tetrabromo-3,6-diphenylbenzene in three steps. The X-ray structure of the deep red, highly luminescent 4 shows it to be a D2 -symmetric molecule with an end-to-end twist of 97°. The central acene is encapsulated by the peripheral phenyl substituents, and as a result, the molecule is relatively unreactive and even displays reversible electrochemical oxidation and reduction.

Sterically demanding methoxy and methyl groups in ruthenium complexes lead to enhanced quantum yields for blue light triggered photodissociation.

Ruthenium complexes containing a sterically congested metal center can serve as light activated prodrugs through photo-activated chemotherapy (PACT). In this work, we modified PACT agents containing 6,6'-dihydroxybipyridine (6,6'-dhbp) (Papish et al., Inorg. Chem., 2017, 56, 7519) by replacing it with a sterically bulky isoelectronic ligand, 6,6'-dimethoxybipyridine (6,6'-dmbp). The resulting complexes, [(phen)2Ru(6,6'-dmbp)]Cl2 (2OMe, phen = 1,10-phenanthroline) and [(dop)2Ru(6,6'-dmbp)]Cl2 (3OMe, dop = 2,3-dihydro-[1,4]dioxino[2,3-f][1,10]phenanthroline), have been fully characterized and display enhanced quantum yields for blue light triggered photodissociation of 0.024(6) and 0.0030(2), respectively. We have also synthesized 4OH = [(dmphen)2Ru(4,4'-dhbp)]Cl2 wherein dmphen = 2,9-dimethyl-1,10-phenanthroline and 4,4'-dhbp = 4,4'-dihydroxybipyridine. These ligands enhance steric bulk near the metal center and move the hydroxy groups further from the metal center, respectively. Complex 4OH displays a relatively low quantum yield of 0.0014(2). All of the new complexes (2OMe, 3OMe, 4OH) were tested in breast cancer cells (MDA-MB-231) and were non-toxic (IC50 > 100 µM). This has been interpreted in terms of unfavorable log(Do/w) values and furthermore photodissociation alone is insufficient for cytotoxicity. We also report the crystal structures of 4OH and 2OMe, the thermodynamic acidity of complex 4OH, and the redox potentials for all new complexes.

Molecular Engineering of Near Infrared Absorbing Thienopyrazine Double Donor Double Acceptor Organic Dyes for Dye-Sensitized Solar Cells.

The thienopyrazine (TPz) building block allows for NIR photon absorption in dye-sensitized solar cells (DSCs) when used as a π-bridge. We synthesized and characterized 7 organic sensitizers employing thienopyrazine (TPz) as a π-bridge in a double donor, double acceptor organic dye design. Donor groups are varied based on electron donating strength and sterics at the donor-π bridge bond with the acceptor groups varied as either carboxylic acids or benzoic acids on the π-bridge. This dye design was found to be remarkably tunable with solution absorption onsets ranging from 750 to near 1000 nm. Interestingly, the solution absorption measurements do not accurately approximate the dye absorption on TiO2 films with up to a 250 nm blue-shift of the dye absorption onset on TiO2. This shift in absorption and the effect on electron transfer properties is investigated via computational analysis, time-correlated single photon counting studies, and transient absorption spectroscopy. Structure-performance relationships were analyzed for the dyes in DSC devices with the highest performance observed at 17.6 mA/cm2 of photocurrent and 7.5% PCE for a cosensitized device with a panchromatic IPCE onset of 800 nm.

Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) To Afford New Heteroleptic Dithiolene Complexes.

The scope of direct substitution of the dithiolene ligand from [M(S2C2Ph2)2] [M = Ni2+ (1), Pd2+ (2), Pt2+ (3)] to produce heteroleptic species [M(S2C2Ph2)2Ln] (n = 1, 2) has been broadened to include isonitriles and dithiooxamides in addition to phosphines and diimines. Collective observations regarding ligands that cleanly produce [M(S2C2Ph2)Ln], do not react at all, or lead to ill-defined decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, -S•SC2Ph2, to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions.

Ruthenium Complexes are pH-Activated Metallo Prodrugs (pHAMPs) with Light-Triggered Selective Toxicity Toward Cancer Cells.

Metallo prodrugs that take advantage of the inherent acidity surrounding cancer cells have yet to be developed. We report a new class of pH-activated metallo prodrugs (pHAMPs) that are activated by light- and pH-triggered ligand dissociation. These ruthenium complexes take advantage of a key characteristic of cancer cells and hypoxic solid tumors (acidity) that can be exploited to lessen the side effects of chemotherapy. Five ruthenium complexes of the type [(N,N)2Ru(PL)]2+ were synthesized, fully characterized, and tested for cytotoxicity in cell culture (1A: N,N = 2,2'-bipyridine (bipy) and PL, the photolabile ligand, = 6,6'-dihydroxybipyridine (6,6'-dhbp); 2A: N,N = 1,10-phenanthroline (phen) and PL = 6,6'-dhbp; 3A: N,N = 2,3-dihydro-[1,4]dioxino[2,3-f][1,10]phenanthroline (dop) and PL = 6,6'-dhbp; 4A: N,N = bipy and PL = 4,4'-dimethyl-6,6'-dihydroxybipyridine (dmdhbp); 5A: N,N = 1,10-phenanthroline (phen) and PL = 4,4'-dihydroxybipyridine (4,4'-dhbp). The thermodynamic acidity of these complexes was measured in terms of two pKa values for conversion from the acidic form (XA) to the basic form (XB) by removal of two protons. Single-crystal X-ray diffraction data is discussed for 2A, 2B, 3A, 4B, and 5A. All complexes except 5A showed measurable photodissociation with blue light (λ = 450 nm). For complexes 1A-4A and their deprotonated analogues (1B-4B), the protonated form (at pH 5) consistently gave faster rates of photodissociation and larger quantum yields for the photoproduct, [(N,N)2Ru(H2O)2]2+. This shows that low pH can lead to greater rates of photodissociation. Cytotoxicity studies with 1A-5A showed that complex 3A is the most cytotoxic complex of this series with IC50 values as low as 4 µM (with blue light) versus two breast cancer cell lines. Complex 3A is also selectively cytotoxic, with sevenfold higher toxicity toward cancerous versus normal breast cells. Phototoxicity indices with 3A were as high as 120, which shows that dark toxicity is avoided. The key difference between complex 3A and the other complexes tested appears to be higher uptake of the complex as measured by inductively coupled plasma mass spectrometry, and a more hydrophobic complex as compared to 1A, which may enhance uptake. These complexes demonstrate proof of concept for dual activation by both low pH and blue light, thus establishing that a pHAMP approach can be used for selective targeting of cancer cells.

An Overview Of Photosubstitution Reactions Of Ru(II) Imine Complexes And Their Application In Photobiology And Photodynamic Therapy.

This article is a short review that presents a short review of photosubstitution reactions of Ru(II) imine complexes and illustrates their use in the development of therapeutic agents. The review begins with an overview of the photophysical behavior and common photoreactions of Ru(II) imine complexes, with select examples from the literature since the 1960s. It is followed by a more detailed picture of the application of knowledge gained over the years in the development of Ru(II) complexes for photobiology and photodynamic therapy.

A Facile Electrochemical Reduction Method for Improving Photocatalytic Performance of α-Fe2O3 Photoanode for Solar Water Splitting.

Electrochemical reduction method is used for the first time to significantly improve the photo-electrochemical performance of α-Fe2O3 photoanode prepared on fluorine-doped tin oxide substrates by spin-coating aqueous solution of Fe(NO3)3 followed by thermal annealing in air. Photocurrent density of α-Fe2O3 thin film photoanode can be enhanced 25 times by partially reducing the oxide film to form more conductive Fe3O4 (magnetite). Fe3O4 helps facilitate efficient charge transport and collection from the top α-Fe2O3 layer upon light absorption and charge separation to yield enhanced photocurrent density. The optimal enhancement can be obtained for <50 nm films because of the short charge transport distance for the α-Fe2O3 layer. Thick α-Fe2O3 films require more charge and overpotential than thinner films to achieve limited enhancement because of the sluggish charge transport over a longer distance to oxidize water. Electrochemical reduction of α-Fe2O3 in unbuffered pH-neutral solution yields much higher but unstable photocurrent enhancement because of the increase in local pH value accompanied by proton reduction at a hematite surface.

Micellar Effects on Photoinduced Electron Transfer in Aqueous Solutions Revisited: Dramatic Enhancement of Cage Escape Yields in Surfactant Ru(II) Diimine Complex/[Ru(NH3)6](2+) Systems.

The effect of cationic micelle incorporation on light induced electron transfer, charge separation and back electron transfer between an aqueous electron donor, [Ru(NH3)6](2+), and a series of Ru(II) diimine complex chromophores/acceptors, is presented. The chromophores have the general formula [(bpy)2Ru(LL)](2+) (LL = bpy; 4-R-4'-methyl-2,2'-bpy, R = pentyl (MC5), terdecyl (MC13), heptadecyl (MC17); 4,4'-di(heptadecyl)-2,2'-bpy (DC17)). Of the five chromophores, the MC13, MC17, and DC17 complexes associate with the added micelle forming surfactant, cetyltrimethylammonium bromide (CTAB). Quenching of the luminescence of the bpy and MC5 complexes by [Ru(NH3)6](2+) is unaffected by addition of surfactant, while rate constants for quenching of the MC13 and MC17 complexes are decreased. Cage escape yields following photoinduced electron transfer to generate [(bpy)2Ru(LL)](+) and [Ru(NH3)6](3+) are approximately 0.1 for all the water-soluble chromophores (excluding DC17) in the absence of added CTAB. In the presence of surfactant, the cage escape yields dramatically increase for the MC13 (0.4) and MC17 (0.6) complexes, while remaining unchanged for [Ru(bpy)3](2+) and the MC5 complex. Back electron transfer of the solvent separated ions is also strongly influenced by the presence of surfactant. For the MC13 and MC17 complexes, back electron transfer rate constants decrease by factors of 270 and 190, respectively. The MC5 complex exhibits two component back electron transfer, with the fast component having a rate constant close to that in the absence of surfactant and a slow component nearly 200 times smaller. Results are interpreted in terms of the partitioning of the 2+ and 1+ forms of the chromophores between aqueous and micellar phases. The extended lifetimes of the radical ions may prove useful in coupling the strong reductants formed to kinetically facile catalysts for reduction of water to hydrogen.

Correction: Electron transfer rate modulation in a compact Re(i) donor-acceptor complex.

Correction for 'Electron transfer rate modulation in a compact Re(i) donor-acceptor complex' by Yuankai Yue et al., Dalton Trans., 2015, 44, 8609-8616.

Homoleptic Tris-Diphosphine Re(I) and Re(II) Complexes and Re(II) Photophysics and Photochemistry.

The ligand-to-metal charge transfer state (LMCT) of [(dmpe)3Re](2+) (dmpe = 1,2-bis(dimethylphosphino)ethane) has been demonstrated to be a potent oxidant (E(0)(Re(2+*)/Re(+)) = 2.61 V vs standard calomel electrode). This complex has been traditionally prepared by nontrivial routes in low yields, and very little has been achieved in optimizing the ground state and emission energy properties of the general class of complexes [(PP)3Re](2+) (PP = chelating diphosphine) through phosphine modification. Improved syntheses for Re(I) tris-homoleptic diphosphine complexes [(PP)3Re](+) (PP = 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(diethylphosphino)ethane (depe), bis(dimethylphosphino)methane (dmpm), bis(diphenylphosphino)methane (dppm), Me2PCH2PPh2, 1,3-bis(dimethylphosphino)propane (dmpp), or 1,2-bis(dimethyl-phosphino)benzene (dmpb)) were achieved by single-pot reactions exploiting the reducing potential of the phosphines when reacted with Re(V) oxo-complexes in 1,2-dichlorobenzene at 160-180 °C. Single-electron chemical oxidation of [(PP)3Re](+) yields luminescent Re(II) analogues; appropriate use of Ph3C(+), Cp2Fe(+), or (4-BrC6H4)3N(+) B(C6F5)4(-) salts produced [(PP)3Re](2+) complexes in good yields. Crystallographic trends for the Re(+)/Re(2+) pairs show significantly lengthened Re(2+)-P bonds for [(PP)3Re](2+) relative to the corresponding [(PP)3Re](+) system. The redox and luminescence behavior of the complexes indicates the luminescence is from a ligand P(σ)-to-metal (Re(dπ)) charge transfer ((2)LMCT) state for all the complexes. Structured luminescence at 77 K is postulated to originate from relaxation of the (2)LMCT state into two spin-orbit coupled states: the ground state and a state ∼ 3000 cm(-1) above the ground state. The excited-state reduction potential (Re(II*/I)) for [(depe)3Re](2+) was determined from the free energy dependence of luminescence quenching rate constants. Yields for formation of charge separated ions were determined for three of the complexes with a variety of electron donors. Despite favorable electrostatics, no charge separated ions were observed for radical ion pairs for which the energy of back electron transfer exceeded 1.1 V.

Electron transfer rate modulation in a compact Re(I) donor-acceptor complex.

Formation of the charge transfer state with the rate constant of (10 ps)(-1) has recently been reported for the complex fac-[Re(I)(CO)3(DCEB)(3DMABN)] (ReEBA); where 3DMABN is 3-dimethylaminobenzonitrile, serving as an electron donor, and DCEB is 4,4'-(dicarboxyethyl)-2,2-bipyridine, serving as an electron acceptor (Y. Yue et al., J. Phys. Chem. A, 118, 10407). 3-Pulse UV-pump - IR-pump - IR-probe spectroscopy is used in this work to study how the charge separation reaction in ReEBA to form a ligand to ligand charge transfer state (LLCT) can be modulated by vibrational excitation of various modes of the complex. While no significant rate modulation was found when the cyano group stretching mode of the 3DMABN donor was excited, a sizable effect was found when the ring stretching mode of the DCEB acceptor was excited. The accumulation of the charge separated state (LLCT state) in the 3-pulse experiment was observed as a sharp excited-state vibrational peak of the symmetric stretch of the three facial carbonyl groups, νSS(CO). Modeling indicates that the rate of charge separation is increased by ca. 28% when vibrational excitation is present. The vibronic coupling signal of the bpy ring mode and νSS(CO) as well as the energy transport dynamics from bpy to carbonyl contributed to the 3-pulse signal and was studied as well using the 3-pulse method. Energy transport between the same modes in the ground electronic state was measured by relaxation-assisted two-dimensional infrared (RA 2DIR) spectroscopy. The energy transport times of 4 ± 0.7 and 5 ± 1.5 ps were found for the ground and excited electronic states.

Following Oxygen Consumption in Singlet Oxygen Reactions via Changes in Sensitizer Phosphorescence.

This work reports an examination of singlet oxygen reactions with amino acid substrates by a method involving measurement of the change in phosphorescence intensity of the singlet oxygen sensitizer. The sensitizer, a Ru(II) bipyridyl complex covalently linked to pyrene, has long-lived phosphorescence in N2 purged aqueous solutions (τ0 ~ 20 µs) that is nearly completely quenched by oxygen in aerated solutions. Irradiation of the complex in water containing sub mM concentrations of histidine, tryptophan and methionine results in a dramatic, easily visible increase in the phosphorescence intensity over a period of 10-100 s. Rate constants for singlet oxygen oxidation of each of the substrates can be obtained by using changes in the phosphorescence intensity in initial rate kinetic analysis. Rate constants obtained in this way compare favorably with those reported in the literature. The method represents a very simple approach for obtaining rate constants for singlet oxygen reactions with various substrates and the kinetics can be extended to nonaqueous solvents.

Sn(IV) Schiff base complexes: triplet photosensitizers for photoredox reactions.

We present the synthesis and characterization of a series of four fluorescent Sn(iv) Schiff base complexes, which also possess long-lived triplet excited states. The complexes absorb visible light (λmax = 420 to 462 nm) and the optical properties are easily tunable without laborious synthetic elaboration. The triplet excited states are not luminescent, but can be observed and followed using nanosecond transient absorption spectroscopy. The lifetimes of the triplet excited states are on the order of 500 µs-10 ms in PMMA matrices. The triplet state energies were estimated via energy transfer reactions with a series of organic triplet acceptors. In addition, the photoexcited complexes react with electron donors and acceptors in solution. These results demonstrate the potential for the development of photosensitizers based on main group elements with high spin orbit coupling constants.

Full-electron ligand-to-ligand charge transfer in a compact Re(I) complex.

Ligand-to-ligand charge transfer (LLCT) states in transition metal complexes are often characterized by fractional electron transfer due to coupling of the LLCT state with many other states via the metal. We designed and characterized a compact Re(I) complex that displays essentially full-electron charge transfer in the LLCT excited state. The complex, [Re(DCEB)(CO)3(L)](+) (DCEB = 4,4'-dicarboxyethyl-2,2'-bipyridine), referred to as ReEBA, features two redox active ligands with strong electron accepting (DCEB) and electron donating (L is 3-dimethylaminobenzonitrile (3DMABN)) properties. The lowest energy excited state formed with a ca. 10 ps time constant and was characterized as the full-electron 3DMABN → DCEB LLCT state using time-resolved infrared spectroscopy (TRIR), transient absorption spectroscopy, and DFT computations. Analysis of a range of vibrational modes helped to assign the charge transfer characteristics of the complex. The LLCT state lifetime in ReEBA shows a strong dependence on the solvent polarity and features solvent dependent frequency shifts for several vibrational reporters. The formation of a full-electron LLCT state (∼92%) was enabled by tuning the redox properties of the electron accepting ligand (DCEB) and simultaneously decoupling the redox active group of the electron donating ligand (3DMABN) from the metal center. This strategy is generally applicable for designing compact transition metal complexes that have full-electron LLCT states.