Lowest Excited Electronic States Research Articles

Singlet Oxygen Photophysics: From Liquid Solvents to Mammalian Cells.

Molecular oxygen, O2, has long provided a cornerstone for studies in chemistry, physics, and biology. Although the triplet ground state, O2(X3Σg-), has garnered much attention, the lowest excited electronic state, O2(a1Δg), commonly called singlet oxygen, has attracted appreciable interest, principally because of its unique chemical reactivity in systems ranging from the Earth's atmosphere to biological cells. Because O2(a1Δg) can be produced and deactivated in processes that involve light, the photophysics of O2(a1Δg) are equally important. Moreover, pathways for O2(a1Δg) deactivation that regenerate O2(X3Σg-), which address fundamental principles unto themselves, kinetically compete with the chemical reactions of O2(a1Δg) and, thus, have practical significance. Due to technological advances (e.g., lasers, optical detectors, microscopes), data acquired in the past ∼20 years have increased our understanding of O2(a1Δg) photophysics appreciably and facilitated both spatial and temporal control over the behavior of O2(a1Δg). One goal of this Review is to summarize recent developments that have broad ramifications, focusing on systems in which oxygen forms a contact complex with an organic molecule M (e.g., a liquid solvent). An important concept is the role played by the M+•O2-• charge-transfer state in both the formation and deactivation of O2(a1Δg).

An Exhaustive Quantum-Classical Study of C6F6+ Using the Newly Formulated Parallel TDDVR Method.

We recently implemented our parallelized quantum-classical dynamical approach, known as the Time-Dependent Discrete Variable Representation (TDDVR) method, which is applied to the spectroscopically important hexafluorobenzene (HFBz) radical cation, where several conical intersections exist in their seven lowest excited electronic states (S11B2u, S21E1g, S31B1u, S41E1u, and S51A2u) considering degeneracy among potential energy surfaces (PESs), to demonstrate their various dynamical aspects. This new parallel version shows almost linear scalability with increasing number of computing processors. To get photoelectron (PE) spectra, Mass-Analyzed Threshold Ionization (MATI) spectra, population dynamics, and many other dynamical observables, the first-principles dynamics is applied at the state-of-the-art level to the corresponding Hamiltonian, where the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) type interactions are involved in those coupled seven electronic states. The quantum-classical method is used to thoroughly analyze the effects of these couplings on the nuclear dynamics of the involved electronic states, and the findings are compared with those observables obtained from experiments. Intrinsic dynamical properties are explained using the reduced densities of the wave packet (WP) in a coupled electronic manifold. The PE and MATI spectra of HFBz computed using TDDVR are found to be in good agreement with earlier experimental data and other theoretically simulated spectra.

Inversion isomerism induced by the Pseudo Jahn-Teller Effect in X2CE molecules (X = H, F; E = O, S, Se) in their reduced and excited states

The pseudo-Jahn-Teller effect (PJTE) is employed to reveal the origin of molecular geometry changes induced by reduction and excitation, using a series of X2CE molecules (X = H, F, Cl; E = C, S, Se) as examples. Their nuclear configuration is planar with C 2v symmetry in the ground electronic state. However, when reduced, they acquire a nonplanar pyramidal structure with an elongated C-E bond in their ground and lowest excited electronic states 1A2 and 3A2. It is shown that these distortions are due to the PJT mixing of the reference electronic states with appropriate excited states via the b 1 vibrational mode. The PJTE is shown to reasonably parametrize the adiabatic potential energy curve ε(Qb 1) along the instability coordinate Qb 1.

Photoaquation of cis-[Rh(dppz)(phen)Cl2]Cl complex prospective as potential light-activated anti-cancer agent

The photoactivated drug usage in anti-cancer therapy, the working mechanism of which doesn’t rely on the formation of reactive oxygen species, allows reducing damage to healthy tissue by controlling toxicity. For instance, light-activated Rh(III) complexes show nuclease activity after irradiation with UV and visible light. However, literature analysis shows a lack of descriptions of basic photochemical mechanisms. Here we report the study of cis-[Rh(dppz)(phen)Cl2]Cl (DPPZPHEN, dppz is dipyrido[3,2-a:2′,3′-c]phenazine, phen is 1,10-phenanthroline) photochemistry in water solutions using stationary photolysis, nanosecond laser flash photolysis and ultrafast pump–probe spectroscopy. After the irradiation with 308 nm light, DPPZPHEN undergoes aquation, which results in the substitution of one chloride ligand by a water molecule and leads to the formation of [Rh(dppz)(phen)(H2O)Cl]Cl2. UV–vis spectra of complex and capillary electrophoresis data were collected and discussed. Laser flash photolysis (355 nm) demonstrates intermediate absorption attributed to the lowest electronic excited state (triplet) of the initial complex. The study of primary photophysical processes showed a rather complicated behavior of transient absorption, which could be described by a set of four exponential functions. The early photophysical processes were described by the scheme including the formation of two excited states of different natures, namely a dppz-based IL state and an LMCT state.

Chromophore Planarity, -BH Bridge Effect, and Two-Photon Activity: Bi- and Ter-Phenyl Derivatives as a Case Study.

In this work, we have employed electronic structure theories to explore the effect of the planarity of the chromophore on the two-photon absorption properties of bi- and ter-phenyl systems. To that end, we have considered 11 bi- and 7 ter-phenyl-based chromophores presenting a donor-π-acceptor architecture. In some cases, the planarity has been enforced by bridging the rings at ortho-positions by -CH2 and/or -BH, -O, -S, and -NH moieties. The results presented herein demonstrate that in bi- and ter-phenyl systems, the planarity achieved via a -CH2 bridge increases the 2PA activity. However, the introduction of a bridge with the -BH moiety perturbs the electronic structure to a large extent, thus diminishing the two-photon transition strength to the lowest electronic excited state. As far as two-photon absorption activity is concerned, this work hints toward avoiding -BH bridge(s) to enforce planarity in bi- and ter-phenyl systems; however, one may use -CH2 bridge(s) to achieve the enhancement of the property in question. All of these conclusions have been supported by in-depth analyses based on generalized few-state models.

Electronic and spin-rovibrational spectroscopy of the HPS+ cation

Using post Hartree-Fock multi-configuration interaction ab initio approaches, the six (four) doublet (quartet) lowest electronic states of thioxophosphane cation, HPS+, are treated. These electronic states are mapped along the internal coordinates, including the HP, PS distances and in-plane HPS bending angle. Several potential minima are located where long-lived HPS+ ions can be found. Also, computations show that the (X˜2A', 12A", 22A", 22A', 14A' and 14A") states are bound, for which we generate their 3D-potential energy surfaces (3D-PESs). After nuclear motion treatments, we determine the rotational and vibrational constants of these states and the pattern of their rovibrational levels up to 4000 cm−1 above the corresponding vibrational ground state level. For instance, the RCCSD(T)/aug-cc-pV(5 + d)Z anharmonic frequencies of HPS+(X˜2A') are computed ν1 = 2237.7, ν2 = 543.0, ν3 = 686.8 (in cm−1). For the lowest electronic excited state (HPS+(12A")), these frequencies change to ν1 = 2330.5, ν2 = 254.6 and ν3 = 749.6 (in cm−1). Several anharmonic resonances are identified. Besides, a very accurate adiabatic ionization energy of HPS (= 9.3173 eV) is deduced using the (U)CCSDT(Q)/aug-cc-pV(T + d)Z approach and where the core-valence (ΔCV), scalar relativistic (ΔSR) and zero point vibrational energy (ΔZPE) corrections are included. Our spectroscopic data should be useful for identifying this ion in laboratory and in media where reactive collisions between PS/PS+ + H+/H or HP/HP+ + S+/S are taking place.

Spectroscopy and photochemistry of ClSSO.

Sulfur-chlorine cycles play a role in the atmosphere of Venus. It is thought that many sulfur-chlorine bearing molecules could be present in Venus's atmosphere and play an important role in its chemical processes. The goal of this work is to provide new insight into the electronic structure and spectroscopy of the [Cl, S, S, O] molecular system. Eight isomers could be formed, but only three were found to be thermodynamically stable relative to the first dissociation limit. We spectroscopically characterized the two lowest energy stable isomers, C1-ClSSO and trans-ClSSO, using the accurate CCSD(T)-F12/aug-cc-pVTZ method. The dipole moments of the two lowest energy stable isomers are predicted to be 1.90 and 1.60 debye, respectively. The C1-ClSSO isomer is suitable for laser induced fluorescence detection since the lowest excited electronic states absorb in the visible, ∼610 nm, and near UV region, 330 nm. We mapped the evolution of the low-lying excited electronic states along the ClS, SS, and SO bond lengths to find that the production of ClS, SO, or S2O is plausible, whereas the production of ClS2 is not allowed.

Electron affinities and lowest triplet and singlet state properties of para-oligophenylenes (n = 3-5): theory and experiment.

We apply photodetachment-photoelectron spectroscopy to measure the electron affinities and the energetics of the lowest excited electronic states of the neutral molecules para-terphenyl (p3P), para-quaterphenyl (p4P) and para-quinquephenyl (p5P), including especially the triplet states below S1. The interpretation of the experimental data is based on the comparison to calculated 0-0 energies and Dyson norms, using density functional theory and multireference configuration interaction methods, as well as Franck-Condon patterns. The comparison between calculated and experimental vibrational fine-structures reveals a twisted benzoid-like molecular structure of the S0 ground state and nearly planar quinoid-like nuclear arrangements in the S1 and T1 excited states as well as in the D0 anion ground state. For all para-oligophenylenes (ppPs) in this series, at least two triplet states have been identified in the energy regime below the S1 state. The large optical S0-S1 cross sections of the ppPs are rationalised by the nodal structure of the molecular orbitals involved in the transition. The measured electron affinities range from 380 meV (p3P) over 620 meV (p4P) to 805 meV (p5P). A saturation of the electron binding energy with the increasing number of phenyl units is thus not yet in sight.

Spectroscopic detection of the stannylidene (H2C=Sn and D2C=Sn) molecule in the gas phase.

The H2CSn and D2CSn molecules have been detected for the first time by laser-induced fluorescence (LIF) and emission spectroscopic techniques through the B̃1B2-X̃1A1 electronic transition in the 425-400nm region. These reactive species were prepared in a pulsed electric discharge jet using (CH3)4Sn or (CD3)4Sn diluted in high-pressure argon. Transitions to the electronic excited state of the jet-cooled molecules were probed with LIF, and the ground state and low-lying Ã1A2 state energy levels were measured from single vibronic level emission spectra. We supported the experimental studies by a variety of ab initio calculations that predicted the energies, geometries, and vibrational frequencies of the ground and lower excited electronic states. The spectroscopy of stannylidene (H2CSn) is in many aspects similar to that of silylidene (H2CSi) and germylidene (H2CGe).

Perturbed and Activated Decay: The Lifetime of Singlet Oxygen in Liquid Organic Solvents.

Singlet oxygen, O2(a1Δg), the lowest excited electronic state of molecular oxygen, plays an important role in a range of chemical and biological processes. In liquid solvents, the reactions of singlet oxygen with a solute kinetically compete with solvent-mediated deactivation that yields the ground electronic state of oxygen, O2(X3Σg-). In this regard, the key parameter is the solvent-mediated lifetime of singlet oxygen, which embodies fundamental physical principles ranging from intermolecular interactions that perturb the forbidden O2(a1Δg) → O2(X3Σg-) transition to the transfer of oxygen's excitation energy into the vibrational modes of a solvent molecule M. Extensive research performed by the global community on this oxygen-related issue over the past ∼50 years reflects its significance. Unfortunately, a satisfactory quantitative understanding of this unique solvent effect has remained elusive thus far. In temperature-dependent studies, we have quantified the singlet oxygen lifetime in common aromatic and aliphatic organic solvents, including partially deuterated molecules that exploit the H/D solvent isotope effect on the lifetime. We now account for experimental data, including previously intractable data, using a model that exploits both weak and strong coupling in the M-O2 complex to accommodate the roles that M plays to (1) induce the forbidden O2(a1Δg) → O2(X3Σg-) transition and (2) accept the excitation energy of O2(a1Δg). As such, our approach brings us appreciably closer to an accurate and predictive ab initio solution for the long-standing oxygen-dependent problem that, in turn, should be relevant for a host of other molecular systems.

Regiochemistry of Donor Dendrons Controls the Performance of Thermally Activated Delayed Fluorescence Dendrimer Emitters for High Efficiency Solution-Processed Organic Light-Emitting Diodes.

The potential of dendrimers exhibiting thermally activated delayed fluorescence (TADF) as emitters in solution‐processed organic light‐emitting diodes (OLEDs) has to date not yet been realized. This in part is due to a poor understanding of the structure–property relationship in dendrimers where reports of detailed photophysical characterization and mechanism studies are lacking. In this report, using absorption and solvatochromic photoluminescence studies in solution, the origin and character of the lowest excited electronic states in dendrimers with multiple dendritic electron‐donating moieties connected to a central electron‐withdrawing core via a para‐ or a meta‐phenylene bridge is probed. Characterization of host‐free OLEDs reveals the superiority of meta‐linked dendrimers as compared to the already reported para‐analogue. Comparative temperature‐dependent time‐resolved solid‐state photoluminescence measurements and quantum chemical studies explore the effect of the substitution mode on the TADF properties and the reverse intersystem crossing (RISC) mechanism, respectively. For TADF dendrimers with similarly small ∆E ST, it is observed that RISC can be enhanced by the regiochemistry of the donor dendrons due to control of the reorganization energies, which is a heretofore unexploited strategy that is distinct from the involvement of intermediate triplet states through a nonadiabatic (vibronic) coupling with the lowest singlet charge transfer state.

Laser-coolable AcOH+ ion for CP -violation searches

The ${\mathrm{AcOH}}^{+}$ molecular ion is identified as a prospective system to search for $\mathcal{CP}$-violation effects. According to our study ${\mathrm{AcOH}}^{+}$ belongs to the class of laser-coolable polyatomic molecular cations implying a large coherence time in the experiments to study symmetry-violating effects of fundamental interactions. We perform both nuclear and high-level relativistic coupled cluster electronic structure calculations to express the experimentally measurable $\mathcal{T},\mathcal{P}$-violating energy shift in terms of fundamental quantities such as the nuclear magnetic quadrupole moment (MQM), electron electric dipole moment ($e\mathrm{EDM}$) and dimensionless scalar-pseudoscalar nuclear-electron interaction constant. We further express nuclear MQM in terms of the strength constants of $\mathcal{CP}$-violating nuclear forces: quantum chromodynamics vacuum angle $\overline{\ensuremath{\theta}}$ and quark chromo-EDMs. The equilibrium structure of ${\mathrm{AcOH}}^{+}$ in the ground and the four lowest excited electronic states was found to be linear. The calculated Franck-Condon factors and transition dipole moments indicate that the laser cooling using an optical cycle involving the first excited state is possible for the trapped ${\mathrm{AcOH}}^{+}$ ions with the Doppler limit estimated to be $\ensuremath{\sim}$4 nK. The lifetime of the ($0,{1}^{1},0$) excited vibrational state considered as a working one for MQM and $e\mathrm{EDM}$ search experiments is estimated to be $\ensuremath{\sim}0.4$ s.

Lowest Triplet and Singlet States in N-Methylacridone and N,N'-Dimethylquinacridone: Theory and Experiment.

In this work, radical anion photodetachment photoelectron (PD-PE) spectra of N-methylacridone (NM-AC) and N,N'-dimethyl-trans-quinacridone (NNM-QAC) are presented, from which we derived electron affinities and transition energies from S0 to the lowest excited triplet and singlet states (T1, T2, and S1). Because in molecules with extended π systems and heteroatoms the state density even in the energy range of the lowest excited electronic states is already high, assignment of most of the spectral structures in the PD-PE spectra was possible only on the basis of theoretical calculations. To this end, adiabatic transition energies including zero-point vibrational energy corrections were determined using a combination of density functional theory, time-dependent density functional theory, and multireference configuration interaction methods. Calculated Franck-Condon spectra proved to be particularly valuable for the assignment of the spectra. Surprisingly, the density of electronically excited states in the low-energy regime is smaller for NNM-QAC than for NM-AC. This is due to the fact that the nπ* energies remain nearly the same in the two molecules whereas the lowest ππ* excited singlet and triplet transitions are strongly red-shifted in going from NM-AC to NNM-QAC.

Molecular structure and properties of MgCa molecule

• Investigation of 13 electronic states using MRCI approach with 4 basis sets. • New assignment of the experimental electronic states. • Spectroscopic and ro-vibrational constants with experimental comparisons. • Franck-Condon factors for vibronic transitions. • Vibrational Branching equipped with calculated lifetimes for laser cooling studies. Experimentally, when the MgCa molecule was studied, certain ambiguity occurred, and an ab initio calculation was requested. For this reason, an extensive study is carried out regarding the electronic structure of MgCa. A new and improved assignment of experimental molecular states is allocated. The accuracy of the adopted ab initio approach is proven in different aspects through our work when agreements are attained between two different experimental approaches and the present work. Theoretical studies of the MgCa compound are performed within the framework of the multi-reference configuration interaction method using 4 different basis sets in order to reach optimal accuracy. The potential energy curves, permanent dipole moments, spectroscopic constants ( T e , ω e , B e , and R e ), and ro-vibrational constants ( G v , B v , D v , R m i n , and R m a x ) are investigated for 13 electronic states. Nine new states are studied here for the first time. The Franck-Condon factors, transition dipole moments at R -centroid, vibrational branching including transition rates, and lifetimes are considered for the states required for laser cooling schemes. Since the focus of this study is devoted to an accurate description of the ground and lowest electronic excited states, we also constructed RKR potentials from the experimental Dunham-type coefficients and computed the spectroscopic and ro-vibrational constants for comparison sake.

Measurements of Metastable Molecules in Nonequilibrium Supersonic Flows

Nonintrusive laser diagnostics are used for the measurements of metastable nitrogen molecules in the lowest excited electronic state, , in a nonequilibrium flow, blowdown supersonic wind tunnel. The tunnel is operated with nitrogen at plenum pressures of Torr, with the flow expanding through a two-dimensional contoured nozzle to the Mach number of . The steady-state run time of the tunnel is approximately 10 s. The flow is excited by a repetitive nanosecond pulse discharge operated in the plenum or in the nozzle throat. Time-resolved absolute populations in the plenum are measured by single-pass, continuous wave tunable diode laser absorption spectroscopy (TDLAS). In the supersonic test section, absolute populations are measured by cavity ring down spectroscopy (CRDS), using a tunable pulsed laser system operated at 10 Hz. During each run, 50 single-shot ring down traces are acquired, demonstrating good shot-to-shot reproducibility. The results demonstrate that the cavity ring down time is not affected by the supersonic flow. populations and the flow temperature are inferred from the single-shot CRDS data. At the conditions when the flow is excited by the discharge in the nozzle throat, population in the supersonic test section is measured by both CRDS and TDLAS diagnostics. The two diagnostic techniques are complementary and can be used for characterization of nonequilibrium reacting flows over a wide range of pressures, including short-run-time high-enthalpy flow facilities.

The Role of Triplet States in the Photodissociation of a Platinum Azide Complex by a Density Matrix Renormalization Group Method.

Platinum azide complexes are appealing anticancer photochemotherapy drug candidates because they release cytotoxic azide radicals upon light irradiation. Here we present a density matrix renormalization group self-consistent field (DMRG-SCF) study of the azide photodissociation mechanism of trans,trans,trans-[Pt(N3)2(OH)2(NH3)2], including spin–orbit coupling. We find a complex interplay of singlet and triplet electronic excited states that falls into three different dissociation channels at well-separated energies. These channels can be accessed either via direct excitation into barrierless dissociative states or via intermediate doorway states from which the system undergoes non-radiative internal conversion and intersystem crossing. The high density of states, particularly of spin-mixed states, is key to aid non-radiative population transfer and enhance photodissociation along the lowest electronic excited states.

Thionitroxyl Radical (H2NS) Isomers: Structures, Vibrational Spectroscopy, Electronic States and Photochemistry

The thionitroxyl radical (H2NS) isomers are characterized using advanced ab initio methodologies. Computations are done using standard and explicitly correlated coupled cluster, CASSCF and MRCI approaches in conjunction with large basis sets, extrapolated to the complete basis set (CBS) limit. The lowest electronic states of different isomers are mapped along the stretching coordinates, thereby confirming the existence of the four already known ground state structures, namely H2NS, H2SN, cis-HNSH and trans-HNSH. Also, it is shown that only the lowest electronic excited states are stable, whereas the upper electronic states may undergo unimolecular decomposition processes forming H + HNS/HSN or the HN + SH or N + H2S or S + NH2 fragments. These data allow an assignment of the deep blue glow observed after reactions between “active nitrogen” and H2S at the beginning of the XXth century. For stable species, a set of accurate structural and spectroscopic parameters are provided. Since small nitrogen-sulfur molecular species are of astrophysical relevance, this work may help for identifying the thionitroxyl radical isomers in astrophysical media and in the laboratory.

Excited-State Engineering in Heteroleptic Ionic Iridium(III) Complexes.

ConspectusIridium(III) complexes have assumed a prominent role in the areas of photochemistry and photophysics due to the peculiar properties of both the metal itself and the ligand environment that can be assembled around it. Ir(III) is larger, heavier, and bears a higher ionic charge than its analogue and widely used d6 ions such as Fe(II) and Ru(II). Accordingly, its complexes exhibit wider ligand-field d–d orbital splitting with electronic levels centered on the metal, typically nonemissive and photodissociative, not playing a relevant role in excited-state deactivations. In other words, iridium complexes are typically more stable and/or more emissive than Fe(II) and Ru(II) systems. Additionally, the particularly strong heavy-atom effect of iridium promotes singlet–triplet transitions, with characteristic absorption features in the UV–vis and relatively short excited-state lifetimes of emissive triplet levels. Ir(III) is also a platform for anchoring ligands of rather different sorts. Its versatile chemistry includes not only coordination with classic N∧N neutral ligands but also the binding of negatively charged chelators, typically having a cyclometalating C∧N anchor. The carbon–metal bond in these systems has some degree of covalent character, but this does not preclude a localized description of the excited states of the related complexes, which can be designated as metal-centered (MC), ligand-centered (LC), or charge transfer (CT), allowing a simplified description of electronic and photophysical properties. The possibility of binding different types of ligands and making heteroleptic complexes is a formidable tool for finely tuning the nature and energy of the lowest electronic excited state of cationic Ir(III) complexes by ligand design. Herein we give an account of our work on several families of iridium complexes typically equipped with two cyclometalating bidentate ligands (C∧N), in combination with mono or bidentate “ancillary” ligands with N∧N, C∧N, and C∧C motifs. We have explored new synthesis routes for both cyclometalating and ancillary ligands, obtaining primarily cationic complexes but also some neutral or even negatively charged systems. In the domain of the ancillary ligands, we have explored isocyanides, carbenes, mesoionic triazolylidenes, and bis-tetrazolic ligands. For the cyclometalating moiety, we have investigated carbene, mesoionic triazolylidene, and tetrazolic systems. Key results of our work include new strategies to modify both cyclometalating and ancillary ligands by relocating ionic charges, the determination of new factors affecting the stability of complexes, a demonstration of subtle structural effects that strongly modify the photophysical properties, new options to get blue-greenish emitters for optoelectronic devices, and a set of ligand modifications allowing the optimization of electrochemical and excited-state properties to obtain new promising Ir(III) complexes for photoredox catalysis. These results constitute a step forward in the preparation of custom iridium-based materials crafted by excited-state engineering, which is achieved through the concerted effort of computational and synthetic chemistry along with electrochemistry and photochemistry.

Singlet fission from upper excited singlet states and polaron formation in rubrene film.

Femtosecond fluorescence up-conversion and transient absorption pump-probe setups are applied to study the relaxation dynamics of the lower and upper excited singlet electronic states in easy-to-make rubrene films. Upon 250 nm (4.96 eV) excitation, singlet fission was observed directly from S2 state bypassing S1 state within 30 fs i.e. breaking the classical Kasha rule. From the transient absorption measurements, polaron formation was also detected on the same time scale. Both singlet fission and polaron formation are accelerated from upper excited states compared with S1 state. Our work shows that rubrene films with low degree of crystallinity could display efficient singlet fission, notably in the case of excitation to upper lying electronic states. This can strongly expand the applications of rubrene in organic electronics. Moreover, our results will provide a new direction for synthesizing novel materials with optimized excited state properties for organic photovoltaic applications.

(Keynote) Radical Ion Excited States As Super-Redox Agents for Artificial Photosynthesis

We will discuss several examples in which photoexcitation of a stable radical anion or cation with visible or NIR light results in production of a high-potential radical ion excited state that can carry out difficult redox reactions relevant to artificial photosynthesis.First, we will show that selective excitation of a naphthalenediimide radical anion (NDI•−) covalently linked to the 4-, 5, or 6-positions of the bipyridine (bpy) in the Re(bpy)(CO)3X (X = Cl or pyridine) carbon dioxide reduction catalyst results in electron transfer from 2*NDI•− to Re(bpy)(CO)3X to form Re(bpy•−)(CO)3X, the first intermediate in the photocatalytic reduction of CO2. Femtosecond UV/Vis, near-IR and mid-IR spectroscopy on these constitutional isomers show that systematically varying the electronic coupling as well as the reaction free energy increases the lifetime of Re(bpy•−)(CO)3X by an order of magnitude when the NDI chromophore is attached to the 6-position of bpy.Electrochemical reduction of the corresponding Mn(bpy)(CO)3X CO2 reduction catalyst is thought to proceed by the initial reduction of MnI to Mn0. We have covalently attached a naphthalenediimide radical anion (NDI•-) chromophore to the 4-, 5-, or 6-positions of the bpy via a phenyl bridge to produce Mn(NDI•--bpy)(CO)3X, where X = Br, CH3CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron transfer reactions following selective photo-excitation of NDI•−. In complexes where NDI•− is attached at the 4- or 5-positions of bipyridine, only the reaction Mn(2*NDI•−-bpy)(CO)3X → Mn(NDI-bpy•−)(CO)3X is observed, while in the complex where NDI•− is attached to the 6-position of bipyridine, the reaction sequence: Mn(2*NDI•−-bpy)(CO)3X → Mn(NDI-bpy•−)(CO)3X → Mn0(NDI-bpy)(CO)3 is observed. Moreover, in the complexes with an NDI•- bound to the 6-position of bipyridine, Mn0(NDI-bpy)(CO)3 exhibits a lifetime that is ~105 times longer than those in complexes with an NDI•- bound at the 4- or 5- positions of the bipyridine.On the oxidative side, we will discuss the 10-phenyl-10H-phenothiazine radical cation (PTZ+•), which has a manifold of excited doublet states accessible using visible and NIR light that can serve as super-photo-oxidants with excited state potentials is excess of +2.1 V vs SCE to power energy demanding oxidation reactions. Photo-excitation of PTZ+• in CH3CN with a 517 nm laser pulse populates a Dn electronically excited doublet state that decays first to the unrelaxed lowest electronic excited state, D1' (τ < 0.3 ps), followed by relaxation to D1 (τ = 10.9 ± 0.4 ps), which finally decays to D0 (τ = 32.3 ± 0.8 ps). D1' can also be populated directly using a lower energy 900 nm laser pulse, which results in a longer D1' → D1 relaxation time (τ = 19 ± 2 ps). To probe the oxidative power of PTZ+• photoexcited doublet states, PTZ+• was covalently linked to each of three hole acceptors, perylene (Per), 9,10-diphenyl-anthracene (DPA), and 10-phenyl-9-anthracene-carbonitrile (ACN), which have oxidation potentials of 1.04, 1.27, and 1.6 V vs. SCE, respectively. In all cases, photoexcitation of PTZ+• result in ultrafast oxidation of Per, DPA, and ACN.The photoexcited peri-xanthenoxanthene radical cation (PXX+•) is another super-oxidant that has a 124 ps electronic excited state (D1) lifetime and can deliver +2.1 V vs. SCE of oxidizing potential. Photoexcitation of PXX+• covalently attached to electron deficient 9,10-bis(trifluoromethyl)anthracene (TMFA) using an 885 nm laser pulse drives oxidation of TFMA with unity quantum yield. Extending the PXX+•-TFMA dyad to a molecular triad having a 9,10-diphenylanthracene terminal hole acceptor, PXX+•-TFMA-DPA, and selectively exciting PXX+• results in formation of PXX-TFMA-DPA+• with a 46% quantum yield and a τ = 11.5 ± 0.6 ns lifetime. This work demonstrates that the PXX+• D1 electronic excited state can serve as a promising super-oxidant for challenging oxidation reactions relevant to solar-energy applications.