Biradical Ground State Research Articles

Observation of SOMO-HOMO Inversion in a Neutral Polycyclic Conjugated Hydrocarbon.

We report the generation of a nonbenzenoid polycyclic conjugated hydrocarbon, which consists of a biphenyl moiety substituted by indenyl units at the 4,4' positions, on ultrathin sodium chloride films by tip-induced chemistry. Single-molecule characterization by scanning tunneling and atomic force microscopy reveals an open-shell biradical ground state with a peculiar electronic configuration wherein the singly occupied molecular orbitals (SOMOs) are lower in energy than the highest occupied molecular orbital (HOMO).

Metal-Ligand Exchange Coupling Alters the Open-Shell Ligand Electronic Structure in a Bis(semiquinone) Complex.

The electronic structure of the bis(dioxolene) bridging ligand -SQ2Th2- is responsive to metal-ligand magnetic exchange coupling. Comparison of the crystal structure of (NiSQ)2Th2 to that of (ZnSQ)2Th2 indicates an open-shell biradical ground state for the dinuclear Ni(II) complex compared to the closed-shell quinoidal character found in the dinuclear Zn(II) complex. Consistent with a comparison of bond lengths obtained by X-ray diffraction, the analysis of the variable-temperature magnetic susceptibility data for crystalline (NiSQ)2Th2 yields reduced SQ-SQ radical-radical magnetic exchange coupling (JSQ-SQ = -203 cm-1) compared to that of (ZnSQ)2Th2 (JSQ-SQ = -321 cm-1). The reduced SQ-SQ exchange coupling in (NiSQ)2Th2 derives from an attenuation of the SQ spin densities, which in turn is derived from the Ni-SQ antiferromagnetic exchange interactions. This reduction in SQ--SQ exchange that we observe for (NiSQ)2Th2 correlates with an effective lengthening of the bridge unit by ∼2.1 Å relative to that of (ZnSQ)2Th2. This magnitude of the effective increase in the bridge distance is consistent with the (NiSQ)2Th2 JSQ-SQ value lying between those of (ZnSQ)2Th2 and (ZnSQ)2Th3. The ability to modulate spin populations on an organic radical via pairwise Ni-SQ magnetic exchange interactions is a general way to affect electronic coupling in the Th-Th bridge. Our results suggest that metal-radical exchange coupling represents a powerful mechanism for tuning organic molecular electronic structure, with important implications for molecular electronics and molecular electron transport.

Hybrid Inorganic-Organic Cross-Metathesis between Diborenes and Acetylene.

The ruthenium-catalyzed cross-metathesis of alkenes and alkynes, which splits the alkene C═C double bond and couples one-half to each carbon of the alkyne C≡C triple bond, is one of the most efficient tools for the synthesis of 1,3-dienes, with wide-ranging applications, including pharmaceutical and polymer chemistry. In contrast, inorganic main-group metathesis reactions are restricted to a handful of examples of heavier p-block multiple bonds (P═P, Ge═Ge, and E≡E, E = Ge, Sn, Pb). We now report the first examples of thermally induced, transition-metal-free cross-metathesis between an organic alkyne and inorganic cyclic alkyl(amino)carbene (CAAC)-stabilized B═B double bonds, which yield fully planar, π-delocalized 1,8-diaza-3,6-diboraoctatetraenes. Density functional theory studies show that these compounds have an open-shell singlet biradical ground state with a thermally accessible closed-shell state. In-depth computational mechanistic analyses show that they are formed via a biradical cycloaddition-cycloreversion mechanism. Finally, unlike their organic counterparts, these B,N-analogues of octatetraene can undergo two-electron chemical reduction to form diamagnetic dianions.

A Stable π-Conjugated Singlet Biradical.

A large polycyclic hydrocarbon with a singlet biradical ground state has been obtained by the combined effects of topology and electron-accepting aromatic substituents, which stabilize its open-shell singlet state.

Towards Magnetic Carbo-meric Molecular Materials.

Numerous studies have underlined the putative diradical character of π-conjugated molecules that can be described by closed-shell Lewis structures, for instance, p-dimethylene p-n phenylenes, or long polyacenes. In the latter compounds, the only way to save the aromaticity of the six-membered rings is to give up the Lewis electron pairing in the singlet biradical ground state. The present work considers the possibility of doing the same by using the basic C2 units of carbo-meric architectures. A series of acyclic and cyclic carbo-meric architectures is studied by using UB3LYP DFT broken-symmetry calculations, including spin decontaminations and subsequent geometry optimization of the singlet diradical. The C2 units are shown to stabilize the singlet biradical by spin delocalization, two of them playing approximately the same role as one radical-insulating 1,4 phenylene moiety. The results are generalized to the investigation of open-shell polyradical singlet states of rigid hydrocarbon structures, the symmetry and rigidity of which can assist cooperativity and self spin polarization effect. Several synthesis targets with challenging magnetic/spin properties are suggested in the carbo-mer series.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties

AbstractUnprecedented neutral perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4‐hydroxyaryl‐substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open‐shell singlet biradical ground state for the PBI biradical OS‐2.. (〈s2〉=1.2191) with a relatively small singlet–triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties.

Unprecedented neutral perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4-hydroxyaryl-substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open-shell singlet biradical ground state for the PBI biradical OS-2(..) (〈s(2)〉=1.2191) with a relatively small singlet-triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

ChemInform Abstract: Zethrenes, Extended P‐Quinodimethanes, and Periacenes with a Singlet Biradical Ground State

AbstractReview: 59 refs.

Indolo[2,3-b]carbazoles with tunable ground states: how Clar's aromatic sextet determines the singlet biradical character

Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet–triplet energy gap (ΔES–T ≅ −1.78 kcal mol−1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future.

Highly Twisted 1,2:8,9-Dibenzozethrenes: Synthesis, Ground State, and Physical Properties

Two soluble and stable 1,2:8,9-dibenzozethrene derivatives (3 a,b) are synthesized through a palladium-catalyzed cyclodimerization reaction. X-ray crystallographic analysis shows that these molecules are highly twisted owing to congestion at the cove region. Broken-symmetry DFT calculations predict that they have a singlet biradical ground state with a smaller biradical character and a large singlet–triplet energy gap; these predictions are supported by NMR and electronic absorption measurements. They have small energy gaps and exhibit far-red/near-infrared absorption/emission and amphoteric redox behaviors.

Zethrenes, extended p-quinodimethanes, and periacenes with a singlet biradical ground state.

Researchers have studied polycyclic aromatic hydrocarbons (PAHs) for more than 100 years, and most PAHs in the neutral state reported so far have a closed-shell electronic configuration in the ground state. However, recent studies have revealed that specific types of polycyclic hydrocarbons (PHs) could have a singlet biradical ground state and exhibit unique electronic, optical, and magnetic activities. With the appropriate stabilization, these new compounds could prove useful as molecular materials for organic electronics, nonlinear optics, organic spintronics, organic photovoltaics, and energy storage devices. However, before researchers can use these materials to design new devices, they need better methods to synthesize these molecules and a better understanding of the fundamental relationship between the structure and biradical character of these compounds and their physical properties. Their biradical character makes these compounds difficult to synthesize. These compounds are also challenging to physically characterize and require the use of various experimental techniques and theoretic methods to comprehensively describe their unique properties. In this Account, we will discuss the chemistry and physics of three types of PHs with a significant singlet biradical character, primarily developed in our group. These structures are zethrenes, Z-shaped quinoidal hydrocarbons; hydrocarbons that include a proaromatic extended p-quinodimethane unit; and periacenes, acenes fused in a peri-arrangement. We used a variety of synthetic methods to prepare these compounds and stabilized them using both thermodynamic and kinetic approaches. We probed their ground-state structures by electronic absorption, NMR, ESR, SQUID, Raman spectroscopy, and X-ray crystallography and also performed density functional theory calculations. We investigated the physical properties of these PHs using various experimental methods such as one-photon absorption, two-photon absorption, transient absorption spectroscopy, electrochemistry, and spectroelectrochemistry. These systematic studies revealed that aromaticity played a very important role in determining their singlet biradical character, which is critically related to both their physical properties and their chemical reactivity. In particular, we found that Clar's aromatic sextet rule, which is useful for the closed-shell PAHs, can also predict the relative biradical character of benzenoid PH-based singlet biradicaloids. Other factors, such as structural flexibility of the biradical and quinoid resonance forms and the participation of the substitution in the π-conjugation, also influence the biradical character. These molecular materials demonstrate a number of unique properties such as near-infrared absorption, redox amphotericity, large two-photon absorption cross section, short excited state lifetime, stimuli-responsive magnetic activity, and singlet fission, which suggests promise for future applications.

Para-Quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: the effect of the fusion mode on the ground states and physical properties.

Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcal mol(-1)), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds.

Cyclic alkyl(amino) carbene stabilized biradical of disilicontetrachloride.

One and a half decades ago the formation of Si2Cl4 from the intermediate species SiCl2 was theoretically predicted to be exothermic. The hypothetical Si2Cl4 has never been experimentally synthesized and isolated. Herein, we report that the Si2Cl4 species was stabilized as singlet biradical (Cy-cAAC·)2Si2Cl4 utilizing two cAAC (cyclic alkyl(amino) carbene). This compound is stable, isolable, and storable at rt under an inert atmosphere. The electronic structure and bonding were studied by theoretical calculations which revealed that the molecule possesses a singlet biradical ground state with an unpaired electron on each carbene C atom having opposite spin.

Compactly Fused o‐Quinone‐Extended Tetrathiafulvalene‐o‐Quinone Triad – a Redox‐Amphoteric Ligand

AbstractA new redox‐amphoteric ligand comprising a p‐phenylene‐extended tetrathiafulvalene (TTF) core and two o‐quinone termini has been synthesized. This work was performed in an attempt to synthesize a bridging ligand by combining one of the most powerful organic donors with strong acceptor units in a single molecule. The product was isolated in the doubly reduced diprotonated form. An X‐ray diffraction study revealed a rigid and planar structure for this molecule. This is the first example of an air‐stable p‐phenylene‐extended TTF with an unprotected central ring. The diquinone form itself has been prepared by oxidation of the doubly reduced diprotonated species and then characterized in solution. The electronic spectrum of this compound contains an intense peak that corresponds to intramolecular charge transfer. The spectroscopic and structural studies of both compounds were accompanied by DFT calculations. A singlet biradical ground state was predicted for the doubly reduced diprotonated form.

ChemInform Abstract: Benzenoid Polycyclic Hydrocarbons with an Open—Shell Biradical Ground State

AbstractReview: recent progress, from both theoretical and experimental perspectives, on four types of benzenoid polycyclic hydrocarbons with an open‐shell biradical ground state: 1) acenes, 2) periacenes and anthenes, 3) zethrenes, and 4) extended p‐quinodimethane derivatives; 63 refs.

A kinetically blocked 1,14:11,12-dibenzopentacene: a persistent triplet diradical of a non-Kekulé polycyclic benzenoid hydrocarbon

The synthesis of high-spin polycyclic hydrocarbons is very challenging due to their extremely high reactivity. Herein, we report the synthesis and characterization of a kinetically blocked 1,14:11,12-dibenzopentacene, DP-Mes, which represents a rare persistent triplet diradical of a non-Kekule polycyclic benzenoid hydrocarbon. In contrast to its structural isomer 1,14:7,8-dibenzopentacene (heptazethrene) with a singlet biradical ground state, DP-Mes is a triplet diradical as confirmed by ESR and ESTN measurements and density functional theory calculations. DP-Mes also displays intermolecular antiferromagnetic spin interactions in solution at low temperature.

Electronic and Exchange Coupling in a Cross-Conjugated D–B–A Biradical: Mechanistic Implications for Quantum Interference Effects

A combination of variable-temperature EPR spectroscopy, electronic absorption spectroscopy, and magnetic susceptibility measurements have been performed on Tp(Cum,Me)Zn(SQ-m-Ph-NN) (1-meta) a donor-bridge-acceptor (D-B-A) biradical that possesses a cross-conjugated meta-phenylene (m-Ph) bridge and a spin singlet ground state. The experimental results have been interpreted in the context of detailed bonding and excited-state computations in order to understand the excited-state electronic structure of 1-meta. The results reveal important excited-state contributions to the ground-state singlet-triplet splitting in this cross-conjugated D-B-A biradical that contribute to our understanding of electronic coupling in cross-conjugated molecules and specifically to quantum interference effects. In contrast to the conjugated isomer, which is a D-B-A biradical possessing a para-phenylene bridge, admixture of a single low-lying singly excited D → A type configuration into the cross-conjugated D-B-A biradical ground state makes a negligible contribution to the ground-state magnetic exchange interaction. Instead, an excited state formed by a Ph-NN (HOMO) → Ph-NN (LUMO) one-electron promotion configurationally mixes into the ground state of the m-Ph bridged D-A biradical. This results in a double (dynamic) spin polarization mechanism as the dominant contributor to ground-state antiferromagnetic exchange coupling between the SQ and NN spins. Thus, the dominant exchange mechanism is one that activates the bridge moiety via the spin polarization of a doubly occupied orbital with phenylene bridge character. This mechanism is important, as it enhances the electronic and magnetic communication in cross-conjugated D-B-A molecules where, in the case of 1-meta, the magnetic exchange in the active electron approximation is expected to be J ~ 0 cm(-1). We hypothesize that similar superexchange mechanisms are common to all cross-conjugated D-B-A triads. Our results are compared to quantum interference effects on electron transfer/transport when cross-conjugated molecules are employed as the bridge or molecular wire component and suggest a mechanism by which electronic coupling (and therefore electron transfer/transport) can be modulated.

Tetracyanoquaterrylene and Tetracyanohexarylenequinodimethanes with Tunable Ground States and Strong Near‐Infrared Absorption

Biradicaloids based on quinoidal rylenes! Soluble and stable tetracyanoquaterrylenequinodimethane (QR-CN) and tetracyanohexarylenequinodimethane (HR-CN) were synthesized. QR-CN has a closed-shell quinoidal structure in the ground state, whereas HR-CN has a singlet biradical ground state. Both compounds showed very strong one-photon and two-photon absorption in the NIR range.

Benzenoid Polycyclic Hydrocarbons with an Open–Shell Biradical Ground State

This Focus Review describes the recent progress, from both theoretical and experimental perspectives, on four types of benzenoid polycyclic hydrocarbons with an open-shell biradical ground state: 1) acenes, 2) periacenes and anthenes, 3) zethrenes, and 4) extended p-quinodimethane derivatives. These interesting molecules have provided excellent platforms to investigate the electronic structures of nanographenes and represent promising candidates for the next generation of molecule-based materials in the field of electronics, spintronics, and non-linear optics. The focus of this article will be put on the structural significance, the physical properties relevant to the open-shell electronic configurations, and potential applications.

Kinetically Blocked Stable Heptazethrene and Octazethrene: Closed-Shell or Open-Shell in the Ground State?

Polycyclic aromatic hydrocarbons with an open-shell singlet biradical ground state are of fundamental interest and have potential applications in materials science. However, the inherent high reactivity makes their synthesis and characterization very challenging. In this work, a convenient synthetic route was developed to synthesize two kinetically blocked heptazethrene (HZ-TIPS) and octazethrene (OZ-TIPS) compounds with good stability. Their ground-state electronic structures were systematically investigated by a combination of different experimental methods, including steady-state and transient absorption spectroscopy, variable temperature NMR, electron spin resonance (ESR), superconducting quantum interfering device (SQUID), FT Raman, and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. All these demonstrated that the heptazethrene derivative HZ-TIPS has a closed-shell ground state while its octazethrene analogue OZ-TIPS with a smaller energy gap exists as an open-shell singlet biradical with a large measured biradical character (y = 0.56). Large two-photon absorption (TPA) cross sections (σ((2))) were determined for HZ-TIPS (σ((2))(max) = 920 GM at 1250 nm) and OZ-TIPS (σ((2))(max) = 1200 GM at 1250 nm). In addition, HZ-TIPS and OZ-TIPS show a closely stacked 1D polymer chain in single crystals.