Hubbry Logo
DiradicalDiradicalMain
Open search
Diradical
Community hub
Diradical
logo
7 pages, 0 posts
0 subscribers
Be the first to start a discussion here.
Be the first to start a discussion here.
Diradical
Diradical
Diradical
View on Wikipedia
from Wikipedia

In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate.[1][2] The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and non-Kekulé molecules that are rarely isolated. Diradicals are even-electron molecules but have one fewer bond than the number permitted by the octet rule.

Examples of diradical species can also be found in coordination chemistry, for example among bis(1,2-dithiolene) metal complexes.[3][4]

Spin states

[edit]

Diradicals are usually triplets. The phrases singlet and triplet are derived from the multiplicity of states of diradicals in electron spin resonance: a singlet diradical has one state (S=0, Ms=2*0+1=1, ms=0) and exhibits no signal in EPR and a triplet diradical has 3 states (S=1, Ms=2*1+1=3, ms=-1; 0; 1) and shows in EPR 2 peaks (if no hyperfine splitting). The triplet state has total spin quantum number S=1 and is paramagnetic.[5] Therefore, diradical species display a triplet state when the two electrons are unpaired and display the same spin. When the unpaired electrons with opposite spin are antiferromagnetically coupled, diradical species can display a singlet state (S=0) and be diamagnetic.[6]

Examples

[edit]

Stable, isolable, diradicals include singlet oxygen and triplet oxygen. Other important diradicals are certain carbenes, nitrenes, and their main-group elemental analogues.[7] Lesser-known diradicals are nitrenium ions, carbon chains,[8] and organic so-called non-Kekulé molecules in which the electrons reside on different carbon atoms. Main-group cyclic structures can also exhibit diradicals, such as disulfur dinitride, or diradical character, such as diphosphadiboretanes. In inorganic chemistry, both homoleptic and heteroleptic 1,2-dithiolene complexes of d8 transition metal ions show a large degree of diradical character in the ground state.[3]

Diradicals in which the unpaired electrons nevertheless interact are sometimes referred to as diradicaloids.

References

[edit]

Further reading

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Diradical

View on Grokipedia
from Grokipedia
A diradical is a molecular species with two unpaired electrons, in which at least two different electronic states with varying multiplicities—such as a singlet (electron-paired) or triplet (electron-unpaired) state—can be identified, often arising from two degenerate or nearly degenerate molecular orbitals each occupied by one electron. These species are classified based on the locations of their singly occupied molecular orbitals (SOMOs), which determine the ground-state spin multiplicity and influence their behavior as reactive intermediates in organic chemistry. The diradical character (DRC) quantifies the extent to which a exhibits diradical-like properties, ranging from 0 for closed-shell singlets to 1 for pure diradicals with two fully unpaired electrons; this measure, often derived from the weight of doubly excited configurations in the , can be assessed spectroscopically or computationally. High DRC enhances reactivity in processes like dimerization, hydrogen abstraction, and to alkenes, though diradicals often display dual reactivity in their singlet states, differing from monoradicals by showing lower barriers in certain concerted pathways while resembling radicals in stepwise mechanisms. Stability is inversely correlated with DRC, with moderate values (0.1–0.5) enabling persistent species through steric or electronic stabilization, as seen in examples like propane-1,3-diyl (trimethylene) or p-quinodimethane analogues modified with bulky substituents. Organic diradicals are pivotal in pericyclic reactions, such as [2+2] cycloadditions, and serve as models for understanding spin-state dynamics in transition metal-free systems. Their tunable properties—impacted by substituents like electron-donating or withdrawing groups—confer applications in , including , , and batteries, where low-energy singlet-triplet gaps facilitate magnetic switching; in biochemistry, they inform and bioimaging via near-IR absorption. Notable examples include Thiele's hydrocarbons, where electron-rich π-systems yield high-spin ground states, and quinone methides, illustrating how DRC modulates instability to reactivity.

Fundamentals

Definition

A diradical is a molecular species with two unpaired electrons occupying degenerate or near-degenerate molecular orbitals, resulting in an open-shell electronic structure. This configuration distinguishes diradicals from closed-shell molecules, where all electrons are paired in molecular orbitals, and from monoradicals, which contain only a single unpaired electron. The term biradical is often used synonymously, though diradical is the preferred term among specialists. The degree of diradical character in such systems is often quantified by the index yy, which measures the contribution of the diradical (doubly excited) configuration in multireference calculations, such as complete active space self-consistent field methods. Here, y=0y = 0 indicates a closed-shell singlet with no diradical character, while y=1y = 1 denotes a pure diradical state. This index provides a continuous scale for assessing the openness of the shell and the weakness of bonds between the radical sites. Diradicals can be classified based on the types of orbitals housing the unpaired s: σ–σ diradicals, in which both electrons reside in σ orbitals; π–π diradicals, involving π orbitals; and σ–π diradicals, with one electron in a σ orbital and the other in a π orbital. This influences the spatial overlap and reactivity of the .

Historical Development

The foundations of diradical chemistry trace back to the pioneering work on monoradicals by Gomberg, who in 1900 discovered the first stable organic free radical, triphenylmethyl, challenging the tetravalency of carbon and establishing the existence of with unpaired electrons. This influenced subsequent extensions to diradicals, as chemists began exploring molecules with two such centers, building on the radical reactivity patterns observed in Gomberg's experiments. In the 1960s and 1970s, theoretical advancements formalized diradicals as key intermediates in pericyclic reactions, with Lionel Salem playing a central role in elucidating their electronic structure and reactivity. Salem's work distinguished between homo- and heterosymmetric diradicals based on orbital symmetry. This period marked a shift from empirical observations to quantum mechanical descriptions, highlighting diradicals' role in thermal and photochemical rearrangements. The brought computational milestones that revolutionized diradical research, particularly through the development and application of complete active space self-consistent field (CASSCF) methods, which allowed precise quantification of diradical character by treating multiple configurations in degenerate or near-degenerate orbitals. These multireference techniques, introduced in formulations, enabled accurate calculations of singlet-triplet gaps and spin densities in transient diradicals, bridging theory with spectroscopic evidence and facilitating predictions of stability and reactivity. By the 2000s, focus shifted toward designing stable, isolable diradicals for applications in , driven by their potential in , , and due to tunable spin properties and behavior. Seminal efforts emphasized pi-conjugated systems with minimized radical-radical coupling, achieving high-spin ground states and thermal persistence, which opened avenues for diradical-based conductors and sensors.

Electronic Structure

Spin States

Diradicals, molecules with two unpaired electrons, can exist in various spin states determined by the total SS. The corresponds to S=0S = 0, where the two electrons have opposite spins and are paired in a way that results in zero net spin, while the has S=1S = 1, featuring parallel spins and a net spin of 1. The spin multiplicity, given by the 2S+12S + 1, thus yields 1 for the singlet and 3 for the triplet, reflecting the number of possible spin orientations. In many organic diradicals, the energy difference between the lowest singlet and triplet states, denoted as ΔEST\Delta E_{ST}, is small, often less than 10 kcal/mol, allowing thermal interconversion between these states at accessible temperatures. For instance, in heptazethrene, ΔEST\Delta E_{ST} is approximately 0.94 kcal/mol, favoring a closed-shell singlet ground state. This narrow gap arises from the weak exchange interaction between the radical centers, which can be modulated by molecular geometry and electronic structure. The nature of the in diradicals is influenced by the type of coupling between the unpaired s: through-bond coupling, mediated by σ\sigma- or π\pi-conjugation along the molecular framework, and through-space coupling, involving direct overlap of nonbonding orbitals. Strong antiferromagnetic coupling via these mechanisms stabilizes the by lowering its energy relative to the triplet, whereas weak coupling leads to a triplet , consistent with Hund's rule, which predicts higher spin multiplicity for electrons in degenerate or nearly degenerate orbitals to minimize electron repulsion. In disjoint organic diradicals, where radical orbitals have minimal overlap, the open-shell singlet and triplet states are typically close in energy, though higher-order effects can make the singlet more stable than the triplet, violating Hund's rule. Higher intermediate spin states, such as the (S=2S = 2), are less common in simple organic diradicals but can occur in polynuclear systems or under specific solid-state conditions where multiple unpaired electrons align ferromagnetically. These states highlight the potential for tunable spin multiplicities in advanced organic materials, though organic examples remain rare compared to complexes.

Orbital Configurations

Diradicals exhibit a distinctive electronic structure governed by , featuring two degenerate or near-degenerate non-bonding molecular orbitals (NBMOs) that accommodate the unpaired electrons. These NBMOs, often derived from p-orbitals on the radical centers, possess energies close to zero in the Hückel framework and contribute negligibly to the overall bonding of the , as their occupation neither stabilizes nor destabilizes the framework significantly. In conjugated diradical hydrocarbons, the NBMOs may be disjoint, meaning they occupy mutually exclusive sets of atoms, or nondisjoint, sharing atomic orbitals, which influences the stability and reactivity of the . Within the canonical two-orbital two-electron model for diradicals, the NBMOs—denoted as ψ1\psi_1 and ψ2\psi_2—yield three primary electronic configurations: the diradical state ψ1ψ2\psi_1 \psi_2, where each orbital holds one electron, and the two closed-shell zwitterionic states ψ12\psi_1^2 and ψ22\psi_2^2, characterized by charge separation across the radical sites. The diradical configuration corresponds to the open-shell singlet or triplet states, with the unpaired electrons distributed singly in the NBMOs, while the zwitterionic configurations localize both electrons on one site, creating formal positive and negative charges. This model, foundational to understanding diradical electronic properties, highlights how small energy splittings between the NBMOs determine the preference for diradical versus zwitterionic character. The overlap between the NBMOs in diradicals arises from either through-bond or through-space interactions, which dictate the extent of delocalization and . Through-bond interactions, often σ-type, occur via the intervening atomic framework, such as in linear 1,3-diradicals where the σ-bonds propagate overlap between distant p-orbitals, leading to effects. In contrast, through-space interactions are π-type, involving direct overlap of parallel p-orbitals in close proximity, as seen in cyclic or stacked diradicaloids, and are highly sensitive to and steric factors. These distinct pathways influence the energetic accessibility of the diradical configuration relative to closed-shell alternatives. Molecular symmetry profoundly affects NBMO overlap and the resulting in diradicals. In high-symmetry cases, such as heterosymmetric diradicals, the NBMOs may belong to different irreducible representations, enforcing and nullifying direct overlap. A representative example is the trimethylene diradical (1,3-propanediyl), where the terminal methylene p-orbitals are orthogonal in the perpendicular (0,90°) conformation, minimizing through-space exchange and relying predominantly on through-bond mediation via the central for weak antiferromagnetic interaction. This contributes to the near-degeneracy of the singlet and triplet states, a hallmark of many σ-diradicals.

Physical Properties

Stability

Diradicals exhibit intrinsic instability arising from their high reactivity, primarily due to the presence of two unpaired electrons that facilitate rapid dimerization, recombination, or other decay pathways. As reactive intermediates, many diradicals possess extremely short lifetimes on the order of femtoseconds, as observed in species like the trimethylene diradical, which undergoes ultrafast ring closure or fragmentation. In contrast, stabilized diradicals can persist for hours to days under inert conditions, with some isolable examples remaining viable indefinitely in solution. Several strategies enhance the persistence of diradicals by mitigating their reactivity. Steric hindrance from bulky substituents, such as chlorinated phenyl groups in polychlorinated triphenylmethyl (PTM) diradicals, shields the radical centers and prevents intermolecular interactions. Conjugation through extended π-systems delocalizes the unpaired electrons, reducing spin density at reactive sites; for instance, in zethrene-based diradicals, this dispersion stabilizes the open-shell structure. Matrix isolation at low temperatures, like -160°C for Thiele's , further prolongs lifetimes by restricting molecular motion in a solid host. Thermodynamically, the formation of diradicals from precursors is governed by relatively low bond dissociation energies (BDEs), which reflect the accessibility of these species but also underscore their instability once formed. For example, the N-N BDE in azo compounds, common precursors to diradicals, typically ranges from 30 to 40 kcal/mol, facilitating thermal dissociation into and the diradical fragment. This low barrier contributes to the transient of many diradicals, as the reverse recombination is entropically disfavored. Compared to monoradicals, diradicals are generally less stable owing to the second , which amplifies electron-electron repulsion in the and increases configurational entropy through additional degenerate spin configurations. While monoradicals benefit from a single doublet ground state, diradicals' can further influence persistence, with triplets often exhibiting greater kinetic stability due to spin restrictions on .

Spectroscopic Detection

Electron paramagnetic resonance (EPR) spectroscopy is a primary method for detecting triplet-state diradicals, as it directly probes the spins and reveals characteristic zero-field splitting (ZFS) parameters. The ZFS arises from the dipole-dipole interaction between the two s, resulting in a splitting of the triplet spin sublevels even in the absence of an external . The axial ZFS parameter DD quantifies the separation between the mS=0m_S = 0 and ∣mS∣=1|m_S| = 1 sublevels, while the rhombic parameter EE measures deviations from ; typical values for localized triplet diradicals range from D≈0.02D \approx 0.02 to 0.050.05 cm⁻¹ and small ∣E∣/∣D∣<0.03|E|/|D| < 0.03. For instance, in photochemically generated 1,3-diarylcyclopentanediyl triplet diradicals, EPR spectra in glass at low temperatures show DD values that correlate with substituent effects on spin polarization and diradical delocalization. Ultraviolet-visible (UV-Vis) detects singlet diradicals through their weak absorption bands, often attributed to spin-allowed but symmetry-forbidden transitions influenced by the open-shell character. In singlet diradicals, the two electrons occupy different orbitals with opposite spins, leading to low-intensity absorptions (ε < 100 M⁻¹ cm⁻¹) due to reduced transition moments compared to closed-shell analogs. Time-resolved UV-Vis studies of localized singlet cyclopentane-1,3-diyl diradicals, generated via photolysis, reveal transient bands around 300–400 nm with lifetimes on the order of microseconds, confirming equilibrium with σ-bonded isomers. For short-lived diradicals, matrix isolation combined with Fourier-transform infrared (FTIR) spectroscopy stabilizes reactive species in matrices at cryogenic temperatures (e.g., 10–20 ), allowing vibrational . Matrix-isolated m-benzyne diradicals exhibit distinct C-H stretching modes around 3000 cm⁻¹ and C≡C stretches near 2100 cm⁻¹, shifted from closed-shell counterparts due to the diradical's biradical character. Transient complements this by capturing ultrafast dynamics in solution or gas phase; for example, in verdazyl diradicals, transient spectra show excited-state absorptions in the near-IR (700–900 nm) decaying to the within picoseconds. Computational methods validate experimental spectra by simulating electronic transitions and vibrational frequencies for diradicals, where single-reference approaches often fail due to multiconfigurational character. (TD-DFT), particularly spin-flip variants, predicts UV-Vis and EPR parameters with errors <0.01 cm⁻¹ for triplet diradicals when using range-separated functionals. Multireference methods like complete active space self-consistent field (CASSCF) combined with second-order (CASPT2) accurately reproduce matrix FTIR bands and transient absorptions, as demonstrated for oxyallyl and benzyne diradicals, aiding assignment of spectral features to specific orbital configurations.

Chemical Reactivity

General Mechanisms

Diradicals exhibit reactivity patterns distinct from those of closed-shell species, often involving stepwise mechanisms that proceed through open-shell intermediates rather than fully concerted pathways. In pericyclic reactions, such as [σ2 + σ2] cycloadditions, biradical mechanisms typically involve sequential bond formation and breaking, contrasting with the synchronous orbital overlap characteristic of concerted processes governed by the Woodward-Hoffmann rules. For instance, thermal [2+2] cycloadditions, which are symmetry-forbidden in a suprafacial concerted manner, frequently adopt a diradical pathway where initial radical-like addition leads to a biradical intermediate before ring closure. This stepwise nature allows for greater flexibility in stereochemical outcomes compared to the rigid of concerted pericyclic reactions. A key principle governing diradical reactivity is spin conservation, which dictates that reactions occur between species of compatible spin multiplicities to minimize requirements. Triplet diradicals, possessing two unpaired electrons with parallel spins, preferentially react with other triplet species, such as or triplet carbenes, leading to products that maintain the overall spin state. In contrast, singlet diradicals, with antiparallel spins, interact primarily with closed-shell molecules, enabling pathways like cycloadditions or insertions without spin inversion. This spin-selective behavior arises from the weak spin-orbit interactions in organic systems, ensuring that is kinetically unfavorable under typical conditions. On surfaces (PES), diradicals can manifest as either transition states or true energy minima, depending on the degree of radical center separation and orbital overlap. When the radical centers are well-separated, diradicals often correspond to minima, allowing them to act as persistent intermediates with lifetimes sufficient for observable reactivity. Conversely, in cases of close proximity, they may represent transition states en route to coupled products, with barriers to interconversion between singlet and triplet states influencing the overall pathway. Computational analyses, such as those using coupled-cluster methods, confirm that the PES for diradical features shallow wells or points that differentiate them from the smoother profiles of closed-shell reactions. Unlike monoradicals, which primarily engage in intermolecular abstractions or additions requiring a diffusion-controlled encounter with a partner, diradicals benefit from intramolecular interactions between their two radical centers. This enables unique processes such as to form closed-shell products or , where one center reduces the other, yielding a of oxidized and reduced . These intramolecular modes enhance reactivity efficiency, particularly for singlet diradicals, and contrast with the chain-propagating behavior of monoradicals in radical polymerizations or substitutions.

Specific Reaction Types

Diradicals exhibit a range of specific reaction types, often dictated by their spin multiplicity and the proximity of radical centers. Intramolecular reactions are prominent in 1,3-diradicals, where the two radical sites can couple to form cyclic products. For instance, the trimethylene diradical can undergo closure to in its . Similarly, the singlet butane-1,4-diyl (tetramethylene diradical) can cyclize to cyclobutane, driven by the spin-allowed pairing of electrons, though it can also fragment into two molecules. Intermolecular reactions of diradicals typically involve to unsaturated systems or from substrates. In additions to alkenes, proceed stepwise; for example, the of cyclobutadiene can add to . Singlet diradicals, in contrast, often react concertedly: the singlet trimethylenemethane diradical can undergo [3+2] cyclo to , while singlet cyclobutadiene favors [4+2] cyclo. is another key intermolecular pathway, particularly for ; the trimethylenemethane can abstract from substrates like , and such abstractions can occur from solvent molecules like hydrocarbons under appropriate conditions. Spin-forbidden reactions arise when diradicals in one spin state access pathways typical of another via (ISC), enabling mixed singlet-triplet reactivity. In the trimethylenemethane diradical, ISC facilitates transitions between states with a singlet-triplet gap that can narrow to near zero, allowing triplet species to access singlet-like concerted closures or vice versa. For the tetramethylene diradical, the shows ISC to triplet, resulting in similar abstraction barriers from a donor. These crossings are influenced by conformational factors and spin-orbit coupling, broadening diradical reactivity beyond strict spin conservation. Diradical intermediates play crucial roles in , particularly in enzymatic cascades forming complex scaffolds. In the of tryptophylquinone (TTQ), a diradical intermediate arises from radical coupling involving β-carbons of residues, enabling cross-linking to form the structure essential for bacterial activity. These applications highlight diradicals' utility in constructing stereoselective bonds in bioactive molecules.

Notable Examples

Trimethylene Diradical

The trimethylene diradical, denoted as •CH₂–CH₂–CH₂•, features unpaired electrons localized on the terminal methylene carbons, with these p-orbitals oriented orthogonally in the , minimizing through-bond interactions and stabilizing the open-shell configuration. This orthogonal arrangement contrasts with the planar geometry preferred in the , where the electrons occupy parallel orbitals for maximal exchange stabilization. The energy landscape of the trimethylene diradical reveals a singlet minimum at a twisted , approximately 40° out of plane for the terminal CH₂ groups, while the adopts a planar conformation as its equilibrium . The barrier to rotation around the central C–C bond in the is approximately 5 kcal/mol, allowing facile interconversion between conformers and contributing to the species' reactivity. Computational studies have quantified the significant diradical character with substantial multireference contributions and intermediate coupling between the radical centers. As a prototypical 1,3-diradical, trimethylene plays a central role in the stereomutation of cyclopropane, serving as a key intermediate in the thermal isomerization pathways that lead to geometrical and structural changes without overall decomposition. Ab initio calculations confirm that the diradical's twisted singlet geometry facilitates stereospecific rearrangements, with secondary deuterium isotope effects supporting the involvement of this intermediate in the ring-opening and reclosure steps. Additionally, the trimethylene diradical participates in [2+2] cycloaddition mechanisms, where its orthogonal orbitals enable stepwise radical coupling, as observed in trapping experiments during cyclopropane thermolysis.

Other Organic Diradicals

1,4-Diradicals, such as the tetramethylene diradical (•CH₂CH₂CH₂CH₂•), feature two radical centers separated by two methylene groups and serve as key intermediates in thermal [2+2] reactions and the reverse stereomutation of cyclobutanes. These species exhibit a non-planar, puckered in their to minimize steric repulsion between the terminal methylene groups, influencing their and favoring biradical character over closed-shell forms. In electrocyclic reactions, tetramethylene-like diradicals arise in the conrotatory ring opening of cyclobutenes, where computational studies reveal shallow minima that allow rapid interconversion between conformers, contributing to the observed experimentally. π-Conjugated diradicals, exemplified by o-xylylene (o-quinodimethane), incorporate an ortho-benzene ring with exocyclic methylene groups, enabling extended delocalization of the unpaired electrons across the π-system for enhanced stability. This conjugation recovers in the six-membered ring upon diradical formation, reducing the singlet-triplet energy gap and allowing isolation of substituted derivatives, such as indeno[2,1-a]fluorene, which display significant diradical character and form stable purple solids under inert conditions. Further extension of the π-framework, as in vertically fused o-QDM systems, promotes higher diradical content but increases reactivity toward oxygenation, highlighting the trade-off between delocalization-driven stability and environmental sensitivity. Heteroatom-substituted diradicals, such as those derived from dimers, introduce centers that alter spin distribution and reactivity compared to all-carbon analogs. For instance, aza-m-xylylene diradicals feature aminyl radical sites with increased steric protection from bulky substituents, leading to half-lives on the order of minutes in solution and distinct spectra due to hyperfine coupling from the nucleus. These species exhibit unique properties, including tunable singlet-triplet gaps influenced by the heteroatom's , which facilitates applications in spin-labeled probes, though they remain prone to N-N coupling or insertion reactions characteristic of triplet s. While the focus remains on organic systems, molecular oxygen (O₂) provides a brief inorganic analogy as a triplet diradical with unpaired electrons in antibonding π* orbitals, driving its role in radical chain reactions like in biological contexts.

Generation Methods

Photochemical Approaches

Photochemical methods for generating diradicals rely on irradiation to excite precursor molecules, triggering homolytic bond cleavage that directly forms biradical species. These approaches are particularly effective for producing short-lived, reactive diradicals that can be trapped or observed in subsequent reactions. A key strategy involves the photolysis of cyclic azo compounds, such as 1-pyrazolines, which undergo efficient extrusion of N₂ upon UV excitation to yield 1,3-diradicals. This process typically proceeds through initial population of an , followed by N=N bond homolysis and rapid loss of , often via a diazenyl biradical intermediate. For instance, direct vapor-phase photolysis of 4-methylene-1-pyrazoline at UV wavelengths generates the trimethylenemethane 1,3-diradical, a non-Kekulé species with significant synthetic utility. Quantum yields for denitrogenation in such pyrazolines vary with substitution and solvent viscosity, ranging from 0.12 to 0.88, reflecting competition between irreversible diradical formation and reversible return to the via the diazenyl intermediate. dependence is notable, with shorter UV light (e.g., below 300 nm) favoring higher yields by enhancing the efficiency of the n→π* transition. In conjugated cyclic azo systems, π→π* excitations can also promote closed-shell precursors to diradical states, often at slightly longer UV wavelengths (around 350–400 nm), enabling selective generation under milder conditions. These diradicals exhibit brief lifetimes, typically on the order of nanoseconds, consistent with their role as reactive intermediates rather than stable species. Another established photochemical route is the Norrish Type I α-cleavage of ketones, where UV induces homolysis of the bond between the carbonyl carbon and an adjacent α-carbon, producing acyl-alkyl diradicals. In cyclic ketones like , this yields a ring-opened 1,ω-diradical (e.g., a 1,5- or 1,6-biradical depending on ring size), with the acyl radical at one terminus and the alkyl radical at the other. The reaction is driven by n→π* excitation of the , commonly at 254–313 nm, with quantum yields for cleavage approaching 0.5–1.0 in small rings, highlighting the process's efficiency. For example, studies of cyclic ketones reveal ultrafast () diradical formation, underscoring the concerted nature of the cleavage in strained systems. These acyl-alkyl diradicals can undergo further fragmentation or recombination, influencing product distributions in photolyses.

Thermal and Redox Methods

Thermal dissociation of cyclic peroxides, such as 1,2-dioxetanes and 1,2-dioxanes, is a common method for generating diradicals through homolytic cleavage of the weak O-O bond. In this process, heating the precursor leads to the formation of 1,4-dioxy or 1,6-dioxy diradical intermediates, which can subsequently fragment or rearrange. For example, the thermolysis of 3,3-dibenzyl-1,2-dioxetane proceeds via a 1,4-dioxy diradical intermediate, as evidenced by product analysis and stereochemical studies. Similarly, prostanoid endoperoxide model compounds, including cyclic peroxalates, yield 1,6-diradicals upon activation around 100-150°C. The for O-O bond homolysis in these systems typically ranges from 25-35 kcal/mol, enabling efficient diradical formation at moderate temperatures. Pyrolysis of hydrocarbons at high temperatures (above 1000 K) generates diradicals through C-C bond homolysis, particularly in and formation processes. This method produces reactive π-diradicals as key intermediates, often from hydrogen abstraction or relief in polycyclic aromatic hydrocarbons, facilitating chain reactions and molecular growth. For instance, in conditions, pentagonal rings in aromatic precursors lead to localized π-diradicals that enable barrierless cross-linking. The activation energies for such C-C bond homolysis in contexts are typically 30-50 kcal/mol for initial steps leading to diradical , influenced by strain and resonance stabilization. Redox methods generate diradicals via one-electron oxidation or reduction of closed-shell precursors, often producing charged diradical species like radical cations or anions. Electrochemical oxidation of neutral molecules, such as acceptor-donor-acceptor triads, can yield diradical dications or triradical cations by removing electrons from multiple sites, altering spin coupling and electron delocalization. For example, one-electron oxidation of radical-substituted closed-shell compounds triggers diradical cation formation, with spin density distributions controllable by substituent effects. Reduction of similar precursors can produce diradical anions, as seen in redox-active Lewis pairs that enable tunable diradical character through electron addition. These processes reverse radical dimerization indirectly by destabilizing closed-shell dimers electrochemically, favoring open-shell diradical states under mild conditions.

References

  1. https://goldbook.iupac.org/terms/view/D01765
  2. https://www.mdpi.com/2073-8994/13/8/1448
  3. https://pmc.ncbi.nlm.nih.gov/articles/PMC10336959/
  4. https://pubs.acs.org/doi/10.1021/acs.chemrev.9b00260
  5. https://goldbook.iupac.org/terms/view/B00671
  6. https://pubs.acs.org/doi/10.1021/jp046322x
  7. https://www.acs.org/education/whatischemistry/landmarks/freeradicals.html
  8. http://chemweb.unl.edu/rajca/Gomberg/gomberg.html
  9. https://onlinelibrary.wiley.com/doi/10.1002/anie.197200921
  10. https://pmc.ncbi.nlm.nih.gov/articles/PMC11837749/
  11. https://www.sciencedirect.com/science/article/abs/pii/0301010480800450
  12. https://pubs.aip.org/aip/jcp/article/150/17/174121/198270/CASSCF-linear-response-calculations-for-large-open
  13. https://pubs.acs.org/doi/10.1021/acscentsci.7b00219
  14. https://www.sciencedirect.com/science/article/pii/S2451929420304885
  15. https://pubs.acs.org/doi/10.1021/ar00040a004
  16. https://pmc.ncbi.nlm.nih.gov/articles/PMC4743817/
  17. https://advanced.onlinelibrary.wiley.com/doi/10.1002/adma.201405093
  18. https://pubs.acs.org/doi/10.1021/ci034056z
  19. https://chemistry.as.miami.edu/_assets/pdf/murthy-group/9-diradical-1-salem.pdf
  20. https://pubs.acs.org/doi/10.1021/ar50037a001
  21. https://www.sciencedirect.com/science/article/pii/S0009261424001337
  22. https://old.iupac.org/publications/pac/1973/pdf/3302x0317.pdf
  23. https://www.sciencedirect.com/science/article/abs/pii/S0009261499002638
  24. https://pubs.rsc.org/en/content/articlelanding/1962/tf/tf9625800670
  25. https://pubs.acs.org/doi/10.1021/jo9817422
  26. https://pubs.acs.org/doi/10.1021/ja9925453
  27. https://pubs.rsc.org/en/content/articlelanding/1996/p2/p29960002085
  28. https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201612329
  29. https://pubs.acs.org/doi/10.1021/acs.joc.1c01410
  30. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/1521-3765%252820010504%25297%253A9%253C1837%253A%253AAID-CHEM1837%253E3.0.CO%253B2-T
  31. https://www.mdpi.com/2673-7256/4/4/25
  32. https://pubmed.ncbi.nlm.nih.gov/27353594/
  33. https://pubs.acs.org/doi/10.1021/acs.jpclett.3c02296
  34. https://pubs.acs.org/doi/10.1021/acs.chemrev.8b00244
  35. https://www.researchgate.net/publication/358304145_Spectroscopy_of_Open-Shell_Singlet_Ground-State_Diradicaloids_A_Computational_Perspective
  36. https://doi.org/10.1021/ja00364a004
  37. https://doi.org/10.1021/ja00032a023
  38. https://doi.org/10.1021/ja00757a057
  39. https://pubs.acs.org/doi/10.1021/ja00727a013
  40. https://pubs.acs.org/doi/10.1021/ja00377a059
  41. https://doi.org/10.1002/anie.201101950
  42. https://doi.org/10.1039/C3SC52622D
  43. https://www.researchgate.net/publication/275361605_Aza-m-Xylylene_Diradical_with_Increased_Steric_Protection_of_the_Aminyl_Radicals
  44. https://pubs.acs.org/doi/10.1021/acs.chemrev.3c00406
  45. https://pubs.acs.org/doi/10.1021/ja00450a055
  46. https://pubs.acs.org/doi/10.1021/ja00049a009
  47. https://www.biosynth.com/uploads/News/Dioxetanes_Minireview_WEB_2020.pdf
  48. https://pubs.acs.org/doi/10.1021/jacs.1c05030
  49. https://www.sciencedirect.com/science/article/abs/pii/S0016236123015168
  50. https://pmc.ncbi.nlm.nih.gov/articles/PMC12073237/
  51. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202300269
Add your contribution
Related Hubs
User Avatar
No comments yet.