Ground States Of Radicals Research Articles

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4

The tetraoxido ruthenium(VIII) radical cation, [RuO4 ]+ , should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO4 ]+ , produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO4 ]+ is identified by the chemical shift at the ruthenium M3 edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO4 ]+ to the closed-shell [RuO4 H]+ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO4 ]+ than for [OsO4 ]+ .

Do not forget the Rydberg orbitals.

Within any molecule or cluster containing one or more positively charged sites, families of Rydberg orbitals exist. Free electrons can attach directly, and anionic reagents with low electron binding energy can transfer an electron into one of these orbitals to form a neutral Rydberg radical. The possibilities that such a radical could form a covalent bond either to another Rydberg radical or to a radical holding its electron in a conventional valence orbital are considered. This Perspective overviews two roles that Rydberg radicals can play, both of which have important chemical consequences. Attachment of an electron into excited Rydberg orbitals is followed by rapid (∼10-6s) relaxation into the lowest-energy Rydberg orbital to form the ground state radical. Although the excited Rydberg species are stable with respect to fragmentation, the ground-state species is usually quite fragile and undergoes homolytic bond cleavage (e.g., -R2NH dissociates into -R2N + H or into -RNH + R) by overcoming a very small barrier on its potential energy surface, thus generating reactive radicals (H or R). Here, it is shown that as a result of this fragility, any covalent bonds formed by Rydberg radicals are weak and the molecules they form are susceptible to exothermic fragmentations that involve quite small activation barriers. Another role played by Rydberg species arises when the Coulomb potentials provided by the (one or more) positive site(s) in the molecule stabilize low-energy anti-bonding orbitals (e.g., σ* orbitals of weak σ bonds or low-lying π* orbitals) to the extent that electron attachment into these Coulomb-stabilized orbitals is rendered exothermic. In such cases, the overlap of the Rydberg orbitals on the positive site(s) with the σ* or π* orbitals allows either a free electron or a weakly bound electron to an anionic reagent that is attracted toward the positive site by its Coulomb force to be guided/transferred into the σ* or π* orbital instead. After attaching to such an anti-bonding orbital, bond cleavage occurs again, generating reactive radical species. Because of the large radial extent of Rydberg orbitals, this class of bond cleavage events can occur quite distant from the positively charged group. In this Perspective, several examples of both types of phenomena are given for illustrative purposes.

ICOM formation from radical chemistry: a mechanistic study from cryogenic matrix coupled with IR and EPR spectroscopies

ABSTRACT Interstellar complex organic molecules (iCOMs) have been identified in different interstellar environments including star forming regions as well as cold dense molecular clouds. Laboratory studies show that iCOMs can be formed either in gas phase or in the solid state, on icy grains, from ‘non-energetic’ (atom-addition/abstraction) or energetic (UV-photon, particle bombardments) processes. In this contribution, using a new experimental approach mixing matrix isolation technique, mass spectrometry, and infrared and EPR spectroscopies, we want to investigate the COM formation at 35 K from a complex mixture of ground state radicals trying to draw a general reaction scheme. We photolyse (121 nm) CH3OH diluted in Ar at low temperature (below 15 K) to generate $\mathrm{H^.CO}$, $\mathrm{HO^.CO}$, $\mathrm{^.CH_2OH}$, $\mathrm{CH_3O^.}$, $\mathrm{^.OH}$, and $\mathrm{^.CH_3}$ radicals and ‘free’ H-atoms within the matrix. Radicals have been identified using infrared and EPR spectroscopies. With the disappearance of the Ar matrix (at 35 K), these unstable species are then free to react, forming new species in a solid film. Some recombination products have been detected using infrared spectroscopy and mass spectrometry in the solid film after Ar removal, namely methyl formate (CH3OCHO), glycolaldehyde (HOCH2CHO), ethylene glycol (HOCH2CH2OH), glyoxal (CHOCHO), ethanol (CH3CH2OH), formic acid (HCOOH), dimethyl ether (CH3OCH3), methoxymethanol (CH3OCH2OH), and CH4O2 isomers (methanediol and/or methyl hydroperoxide). The detected molecules are fully consistent with the radicals detected and strongly support the solid state scenario of iCOM formation in interstellar ices based on radical–radical recombination. We then discuss astrophysical implications of the radical pathways on the observed gas phase iCOMs.

Photoelectron photofragment coincidence spectroscopy of aromatic carboxylates: benzoate and p-coumarate.

Photoelectron-photofragment coincidence spectroscopy was used to study the dissociation dynamics of the conjugate bases of benzoic acid and p-coumaric acid. Upon photodetachment at 266 nm (4.66 eV) both aromatic carboxylates undergo decarboxylation, as well as the formation of stable carboxyl radicals. The key energetics are computed using high-level electronic structure methods. The dissociation dynamics of benzoate were dominated by a two-body DPD channel resulting in CO2 + C6H5 + e-, with a very small amount of stable C6H5CO2 showing that the radical ground state is stable and the excited states are dissociative. For p-coumarate (p-CA-) the dominant channel is photodetachment resulting in a stable radical and a photoelectron with electron kinetic energy (eKE) <2 eV. We also observed a minor two-body dissociative photodetachment (DPD) channel resulting in CO2 + HOC6H4CHCH + e-, characterized by eKE <0.8 eV. Evidence was also found for a three-body ionic photodissociation channel producing HOC6H5 + HCC- + CO2. The ion beam contained both the phenolate and carboxylate isomers of p-CA-, but DPD only occurred from the carboxylate form. For both species DPD is seen from the first and second excited states of the radical, where vibrational excitation is required for decarboxylation from the first excited radical state.

Dynamical signatures from competing, nonadiabatic fragmentation pathways of S-nitrosothiophenol.

S-Nitrosothiols (RSNOs) are derived from the combination of sulfur and nitric oxide (NO) radicals in the Earth's atmosphere and fragment to products following photolysis. Extensive theoretical studies have focused on the thermodynamic and, to a lesser extent, photochemical properties of RSNOs. However, experimental studies of these compounds have been limited due to the inherent instability of RSNOs at room temperature. Using velocity map imaging (VMI), we explore the photodissociation dynamics of jet-cooled S-nitrosothiophenol (PhSNO) from 355 nm photolysis. We report the translational and internal energy distributions of the NO and thiophenoxy (PhS) co-fragments, which are determined by spatial detection of the ionized NO photofragments using 1+1 resonance-enhanced multiphoton ionization (REMPI). The velocity distributions indicate competing PhSNO nonadiabatic dissociation pathways, in which PhS is formed in the ground and first excited electronic states when probing high- and low-energy NO (X2Π1/2, v'', J'') rovibrational states, respectively. The results of multireference electronic structure calculations suggest that direct dissociation on the bright S2 state results in PhS formed in its excited electronic state, whereas intersystem crossing into the triplet manifold leads to population of PhS in its electronic ground state. The dynamical signatures from the dissociation processes are imprinted on the fragments' quantum states and relative translation, which we explore in rigorous detail using state-resolved imaging and high-level theoretical calculations.

Formally Ferric Heme Carbon Monoxide Adduct.

Formally ferric carbonyl adducts are reported in a series of thiolate-bound iron porphyrins. Resonance Raman data indicate the presence of both Fe-S and Fe-CO bonds, and EPR data of this S = 1/2 species indicate a ligand-based electron hole, giving this complex an Fe(II)-thiyl radical electronic ground state. The FTIR data show that the C-O vibrations are substantially higher than in the corresponding ferrous-thiolate CO adducts. DFT calculations reproduce the spectroscopic features and indicate that backbonding to the low lying π* orbitals of the bound CO stabilizes the Fe 3d orbitals resulting in a stabilization of the ferrous-thiyl radical ground state compared to the five-coordinate ferric-thiolate precursor complexes. Access to stable thiyl radicals will help understand these elusive species that are mostly encountered as short-lived reactive reaction intermediates.

A Review on the Origin of Synthetic Metal Radical: Singlet Open-Shell Radical Ground State?

In synthetic metals, free radicals in neutral organic semiconductors are acknowledged as their defects or impurities. However, polycyclic aromatic hydrocarbons (PAHs) with singlet open-shell diradical ground state encourage us to investigate the other potential origin of radicals in neutral organic semiconductors. Herein, for the first time, we observed strong electron spin resonance (ESR) signal in a serials of typical small molecule (SMs). Neutral SMs (NSMs) with strong acceptors including benzothiadiazole, diketopyrrolopyrrole, and naphthalene diimide showed significant ESR signals while they contained strong donors. From the unexpected 1H NMR broadening and increase of ESR signal, we propose TPA-DPP has singlet open-shell ground state and thermally populated triplet species excited via rising temperature, which represent our new viewpoints different from previous reports. The intensity of the ESR signals and singlet–triplet energy gap of the NSMs are related to their electronic delocalization effect a...

Reaction mechanism and product branching ratios of the CH + C3H4 reactions: a theoretical study.

Two ground-state CH radical reactions with the C3H4 isomers allene and methylacetylene occurring along the C4H5 potential energy surface (PES) were studied to probe the reaction mechanisms and final product distributions. The calculations were performed using a CCSD(T)-F12//B2PLYPD3 PES in combination with the 1-D chemical master equation. The reaction between the CH radical and allene was found to lead to exclusive "funneling" of the energized C4H5 intermediates into linear C4H5 configurations before reaching the exit channels, regardless of the specific nature of the initial bimolecular reactive encounter. In the case of the CH radical reaction with methylacetylene, energized C4H5 three-membered ring structures underwent H loss in significant amounts resulting in the production of a cyclic C4H4 methylenecyclopropene product, in accordance with experiments. The theoretical product distribution at room temperature for methylacetylene + CH was ∼35% methylenecyclopropene, ∼36% vinylacetylene, and ∼28% 1,2,3-butatriene, which is in agreement with the available experimental data. The distribution for allene + CH was ∼93% vinylacetylene, ∼4% 1,2,3-butatriene and ∼3% acetylene + vinyl, which overestimates the experimental yield of vinylacetylene and underestimates that of 1,2,3-butatriene by ∼10%. The possible reasons for this slight quantitative deviation of the theoretical results obtained within statistical treatment from the experiment are discussed.

Möbius–Hückel Topology Switching in Expanded Porphyrins: EPR, ENDOR, and DFT Studies of Doublet and Triplet Open-Shell Systems

The one-sided Mobius band topology with its characteristic 180° twist has fascinated and inspired philosophers, artists and scientists since a long time. On the molecular level, only in the last 13 years a few chemistry groups succeeded to artificially create novel compounds with Mobius symmetry by theory-based molecular design and elaborate chemical synthesis. The interest in molecules with Mobius band symmetry was greatly stimulated in 1964 by a theoretical paper by Edgar Heilbronner from the ETH Zurich. He predicted that sufficiently large [n]annulenes with a closed-shell electron configuration of 4n π-electrons should allow for sufficient π-overlap stabilization to be synthesizable by twisting them into the Mobius topology of their hydrocarbon skeleton. In 2003, the first synthesis of an aromatic Mobius annulene was accomplished by Rainer Herges and co-workers in Kiel. In 2007, Lechoslaw Latos-Grazynski and co-workers in Wroclaw succeeded in synthesizing free-base di-p-benzi (Yoneda et al., Angew Chem Int Ed 53: 13169–13173, 2014) hexaphyrin (1.1.1.1.1.1), compound 1, an expanded porphyrin which can dynamically switch between Huckel and Mobius conjugation upon changes of solvent and temperature. Shortly thereafter, in 2008, Atsuhiro Osuka and his co-workers from Kyoto, Seoul and Hyogo published the synthesis of an expanded porphyrin in which metalation triggered the production of molecular twisting and Mobius aromaticity. In this minireview, among other studies also our recent EPR, ENDOR and DFT studies on open-shell states of 1, i.e., on the ground-state radical cation doublet state (total electron spin S = 1/2) and the first excited triplet state (S = 1) are summarized. The review is largely based on a previous joint publication of the current authors with the Latos-Grazynski group on radical cations of 1 (Mobius et al., Phys Chem Chem Phys 17:6644–6652, 2015). The radical cation study was the first one of an open-shell π-system with Mobius topology. In the doublet state, the hyperfine interactions of the unpaired electron spin with specific magnetic nuclei in the molecule was used as a sensitive probe for the electronic structure of the molecule and its symmetry properties. This work has now been extended to state-of-the-art DFT theory studies on photo-excited triplet states of 1. In the open-shell triplet state, besides hyperfine couplings, a change of the zero-field splitting interaction between the two unpaired electron spins is predicted to be a viable sensor for electronic structure changes upon Mobius-to-Huckel topology switching.

Gamma and ion-beam irradiation of DNA: Free radical mechanisms, electron effects, and radiation chemical track structure

The focus of our laboratory's investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ-) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre−), and aqueous (or, solvated) electrons (eaq−)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species.

Kinetic modeling and sensitivity analysis of plasma-assisted oxidation in a H2/O2/Ar mixture

A numerical scheme describing the oxidation process induced by single and multiple dielectric barrier discharges in a H2/O2/Ar mixture is developed. Path flux and sensitivity analyses are performed in order to identify important reaction paths. The analyses are conducted for an initial mixture of 2000 ppm H2 and 3000 ppm O2 balanced in Ar at a constant pressure of 1 atm and temperatures ranging from 474 K to 1008 K, covering both below and above the second explosion limit. Results with only one discharge as well as with repetitive discharges at rates between 1 and 5 kHz are discussed. Three sets of reaction schemes leading to H2O formation are identified: two short-time-scale schemes involving negative ions and O(1D), respectively, and a long-time-scale scheme involving ground state radicals, which is responsible for the majority of the H2O formation and driven by plasma dissociation of H2 and O2. At temperatures below the second explosion limit, the last scheme drives the straight chain propagation mechanism without causing exponential growth of radicals, where the reactions of HO2 play important roles on the overall fuel oxidation. At temperatures above the second explosion limit, H and O atoms produced from the dissociation of reactants by deactivation of excited argon subsequently trigger ignition significantly reducing the ignition delay. The consumption of H2 and O2 which follows is governed by conventional high temperature chain branching kinetics and occurs at a rate equivalent to that of the purely thermal reaction. Increasing the pulse repetition rate of the discharge at low temperatures results in a shift of the rate-limiting steps from reactions of H atoms to those of the OH radical. Furthermore, the kinetics of metastable Ar*m, HO2, O2(a1Δg), and O(1D) are analyzed and their implications to other systems are discussed.

Free Radical Threshold Value: A New Universal Body Constant

Three evolutionary sources create ‘primary' reactive oxygen species (ROS) and ‘secondary' lipid oxygen species (LOS), forming the human body's ‘free radical ground state'. We present evidence for the existence of a universal free radical threshold value (FRTV), defining the borderline between advantageous and adverse effects of free radicals observed above the free radical ground state. Based on standard vitamin D doses, the calculated amount of ∼3.5 × 10¹² rad/mg ROS/LOS tissue represents the tolerated number of free radicals in skin tissue - defined as FRTV. By means of quantitative ESR x-band spectroscopy, the FRTV was experimentally verified using ex vivo human skin irradiated with ultraviolet + visible (UV + VIS), UVB + UVA and VIS light. In addition, we investigated whether this threshold is also existent in internal organs by extending our experiment to fresh porcine liver. Based on the determination of ROS/LOS below and above the FRTV, ROS > LOS was characterized as beneficial and LOS > ROS as deleterious to the organism, respectively. Results of the experiments using porcine liver confirmed the appearance of the FRTV at radical generation ∼3.5 × 10¹² rad/mg. The relation ROS/LOS before and after the FRTV was consistent with the results determined for the skin. We conclude that the FRTV, theoretically calculated and experimentally confirmed, should be considered as a new ‘universal body constant'.

Anion resonances of para-benzoquinone probed by frequency-resolved photoelectron imaging.

The resonant attachment of a free electron to a closed shell neutral molecule and the interplay between the following electron detachment and electronic relaxation channels represents a fundamental but common process throughout chemical and biochemical systems. The new methodology of anion frequency-resolved photoelectron imaging is detailed and used to map out molecular excited state dynamics of gas-phase para-benzoquinone, which is the electron accepting moiety in many biological electron-transfer chains. Three-dimensional spectra of excitation energy, electron kinetic energy, and electron ejection anisotropy reveal clear fingerprints of excited and intermediate state dynamics. The results show that many of the excited states are strongly coupled, providing a route to forming the ground state radical anion, despite the fact that the electron is formally unbound in the excited states. The relation of our method to electron impact attachment studies and the key advantages, including the extension to time-resolved dynamics and to larger molecular systems, are discussed.

Reactions of HOCO radicals through hydrogen-atom hopping utilizing clathrate hydrates as an observational matrix

The carboxyl (HOCO) radical, which is an important species in atmospheric chemistry and combustion, is an intermediate in the reaction: CO + OH → CO2 + H and serves as a hydrogen donor to the reaction partners. The cis-HOCO radical, one of the ground-state HOCO radicals, is supposed to be decomposed into CO2 and the hydrogen atom by a tunneling effect. In order to prove the hypothesis, we performed electron spin resonance (ESR) measurements to investigate the decay mechanisms of the ground-state HOCO and DOCO radicals in gamma-ray-irradiated CO2 hydrates, which may hold the radicals stably. The ground-state HOCO and DOCO radicals decayed according to a second-order decay model and transformed into formic acid and CO2. The ratio of the decay rate constants of HOCO and DOCO radicals shows a good agreement with that in the kinetic isotope effect for the hydrogen and deuterium abstraction reactions. These results indicate that they react with another HOCO radical in the adjacent hydrate cage without the tunneling effect. This implies that the ground-state HOCO radicals are not decomposed by the tunneling effect but are decayed through reactions with some atoms, molecules, and/or radicals even in the gas phase. In addition, the hydrogen-atom hopping through the temporary hydrogen bonds between the HOCO radical and CO2 results in a seeming diffusion of the HOCO radicals in the CO2 hydrate; this would be an important concept for the studies of the radical diffusions and the supply of hydrogen atoms in gas, liquid, and solid phases.

Gas-phase organic reactions of the atomic oxygen radical cation

Reactivity of ground-state oxygen radical cation, O+(4S), has been studied with several organic compounds for the first time. Rate constants and product distributions have been measured for the ion-neutral reactions of O+ with acetaldehyde, acetic acid, acetone, dimethyl ether, methanol, and methyl formate at 300K in a flowing-afterglow-selected ion flow tube (FA-SIFT). The reactions observed proceed efficiently, occurring above 50% of the collision rate in each case. We observed highly exothermic charge transfer reactions which lead to dissociation in some cases. Other interesting trends in reactivity include attack on methyl groups, and for some reactions, O+ replaces the methyl radical.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

Electronic structure of a beryllium half‐sandwich complex, Be(η5‐C5H5)

AbstractAb initio electron propagator calculations on the electron affinities of the $ {\rm Be(\eta ^5-C_5H_5)}^{+} $ complex cation and electron detachment energies of the corresponding anion have been performed at the optimized geometry of the ground state of the neutral species. These results, obtained with a basis set that includes many diffuse and polarization functions, provide the relative energies of doublet states of $ {\rm Be(\eta ^5-C_5H_5)} $. In the former set of calculations, energy differences between the 2A1 ground‐state and various excited doublet states are associated with promotion of an unpaired electron from the 6a1 molecular orbital that consists chiefly of s functions on the Be nucleus to higher Be‐centered molecular orbitals that exhibit various patterns of interference between s, p, and d functions. Differences between electron detachment energies of the anion provide the energy separation between the radical's ground state and an excited state in which an electron is promoted from ligand‐centered π orbitals to 6a1. Dyson orbitals and pole strengths corresponding to correlated electron binding energies calculated with various diagonal self‐energy approximations confirm these qualitative pictures of the electronic structure of the lowest states of $ {\rm Be(\eta ^5-C_5H_5)} $. © 2012 Wiley Periodicals, Inc.

Photoinduced water splitting with oxotitanium porphyrin: a computational study

The photochemistry of the hydrogen-bonded oxotitanium porphyrin-water complex (TiOP-H(2)O) has been explored with electronic-structure calculations. It is shown that intramolecular charge-transfer processes, which are initiated by the excitation of the Soret band of TiOP, accumulate electronic charge on the oxygen atom of TiOP, which in turn abstracts a hydrogen atom from water by an exoenergetic and essentially barrierless hydrogen-transfer reaction, resulting in the TiPOH˙-OH˙ biradical. About 75% of the absorbed photon energy is thus stored as chemical energy in two ground-state radicals. Absorption of a second photon by TiPOH˙ can result in the detachment of the H˙ radical and recovery of the photocatalyzer TiOP. Again, about 75% of the photon energy is stored in the dissociation energy of TiPOH˙. Overall, a water molecule is decomposed into H˙ and OH˙ radicals by the absorption of two visible photons. Exoenergetic radical recombination reactions can yield molecular hydrogen, molecular oxygen or hydrogen peroxide as closed-shell products.

An LIF characterization of supersonic BO (X2Σ+) and CN (X2Σ+) radical sources for crossed beam studies

Various ablation sources generating supersonic boron monoxide (BO; X(2)Σ(+)) radical beams utilizing oxygen (O(2)), carbon dioxide (CO(2)), methanol (CH(3)OH), and water (H(2)O) as seeding gases were characterized in a crossed molecular beams setup by mass resolved time-of-flight spectroscopy and spectroscopically via laser induced fluorescence. Intensities of the sources as well as rovibrational energy distributions were analyzed. The molecular oxygen source was found to produce excessive amount of an unwanted BO(2) byproduct. Internal vibrational energy of boron monoxide generated in the water and methanol sources was too high to be considered for the study of dynamics of ground state radicals. The best combination of intensity, purity, and low internal energy was found in the carbon dioxide source to generate boron monoxide. We successfully tested the boron monoxide (BO; X(2)Σ(+)) radical beam source in crossed beams reactions with acetylene (C(2)H(2)) and ethylene (C(2)H(4)). The source was also compared with supersonic beams of the isoelectronic cyano (CN; X(2)Σ(+)) radical.

Ultrafast Intersystem Crossing and Spin Dynamics of Zincmeso-Tetraphenylporphyrin Covalently Bound to Stable Radicals

tert-Butylphenylnitroxide (BPNO(•)) and α,γ-bisdiphenylene-β-phenylallyl (BDPA(•)) stable radicals are each attached to zinc meso-tetraphenylporphyrin (ZnTPP) at a fixed distance using one of the ZnTPP phenyl groups. BPNO(•) and BDPA(•) are oriented para (1 and 3, respectively) or meta (2 and 4, respectively) relative to the porphyrin macrocycle. Following photoexcitation of 1-4, transient optical absorption spectroscopy is used to observe excited state quenching of (1)*ZnTPP by the radicals and time-resolved electron paramagnetic resonance (TREPR) spectroscopy is used to monitor the spin dynamics of the paramagnetic product states. The presence of BPNO(•) or BDPA(•) accelerates the intersystem crossing rate of (1)*ZnTPP about 10- to 500-fold in 1-4 depending on the structure compared to that of (1)*ZnTPP itself. In addition, the lifetime of (3)*ZnTPP in 1 is shorter than that of (3)*ZnTPP itself as a result of enhanced intersystem crossing (EISC) from (3)*ZnTPP to the ground state. The TREPR spectra of the three unpaired spins produced within 1 and 2 show spin-polarized excited doublet (D(1)) and quartet (Q) states and subsequent formation of a spin-polarized ground state radical (D(0)). All three signals are absorptive for 1 and emissive for 2. Polarization inversion of the Q state is observed on a tens of nanoseconds time scale in 2, while no polarization inversion is observed for 1. The lack of polarization inversion in 1 is attributed to the short lifetime of the doublet-quartet manifold as a result of the very large exchange interaction. The TREPR spectra of 3 and 4 show ground state radical polarization at X-band (9.5 GHz) at room temperature, but not at 85 K, and similarly no polarization is observed at W-band (94 GHz). No evidence of excited doublet or quartet states is observed, indicating that the exchange interaction is both weak and temperature dependent. These results show that although ultrafast EISC produces (3)*ZnTPP within 1-4, the magnitude of the exchange interactions between the three relevant spins in the resulting (3)*ZnTPP-BPNO(•) and (3)*ZnTPP-BDPA(•) systems dramatically alters their spin dynamics.