A Peri‐tetracene Diradicaloid: Synthesis and Properties

Peri‐acenes are good model compounds for zigzag graphene nanoribbons, but their synthesis is extremely challenging owing to their intrinsic open‐shell diradical character. Now, the successful synthesis and isolation of a stable peri‐tetracene derivative PT‐2ClPh is reported; four 2,6‐dichlorophenyl groups are attached onto the most reactive sites along the zigzag edges. The structure was confirmed by X‐ray crystallographic analysis and its electronic properties were systematically investigated by both experiments and theoretical calculations. It exhibits an open‐shell singlet ground state with a moderate diradical character (y₀=51.5 % by calculation) and a small singlet–triplet gap (ΔE_S‐T=?2.5 kcal mol^?1 by SQUID measurement). It displays global aromatic character, which is different from the smaller‐size bisanthene analogue BA‐CF3 .     

Generation of “Sumanenylidene”: A Ground‐State Triplet Carbene on a Curved π‐Conjugated Periphery

We have observed the generation of sumanenylidene ( 2 ), a divalent, neutral‐carbon species at the benzylic position of sumanene ( 1 ). We also clarified both experimentally and theoretically that the ground state of compound 2 was a triplet state and that its singlet–triplet energy gap (ΔE_ST) was similar to that in fluorenylidene. The curved structure of compound 2 led to slightly better spin delocalization over the two adjacent aromatic rings than in planar systems, because of the unpaired spins on the σ and π orbitals. Synthetic application of the carbene precursor, diazosumanene ( 5 ), with a variety of thiocarbonyl compounds revealed its utility for the preparation of tetrasubstituted alkene compounds (e.g., that contain a strongly electron‐donating unit) that are directly conjugated to the sumanene ( 1 ) moiety.     

A high-spin diradical dianion and its bridged chemically switchable single-molecule magnet

Triplet diradicals have attracted tremendous attention due to their promising application in organic spintronics, organic magnets and spin filters. However, very few examples of triplet diradicals with singlet–triplet energy gaps (ΔE_ST) over 0.59 kcal mol⁻¹ (298 K) have been reported to date. In this work, we first proved that the dianion of 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (2,7-tBu₂-PTO) was a triplet ground state diradical in the magnesium complex 1 with a singlet–triplet energy gap ΔE_ST = 0.94 kcal mol⁻¹ (473 K). This is a rare example of stable diradicals with singlet–triplet energy gaps exceeding the thermal energy at room temperature (298 K). Moreover, the iron analog 2 containing the 2,7-tBu₂-PTO diradical dianion was isolated, which was the first single-molecule magnet bridged by a diradical dianion. When 2 was doubly reduced to the dianion salt 2K2, single-molecule magnetism was switched off, highlighting the importance of diradicals in single-molecule magnetism.

We report a triplet diradical dianion in magnesium complex with ΔE_ST = 0.94 kcal mol⁻¹ (473 K). Its iron analog is the first single-molecule magnet bridged by a diradical dianion, and the SMM property is switched off through two-electron reduction.     

Stable Oxindolyl‐Based Analogues of Chichibabin's and Müller's Hydrocarbons

Chichibabin's and Müller's hydrocarbons are classical open‐shell singlet diradicaloids but they are highly reactive. Herein we report the successful synthesis of their respective stable analogues, OxR‐2 and OxR‐3 , based on the newly developed oxindolyl radical. X‐ray crystallographic analysis on OxR‐2 reveals a planar quinoidal backbone similar to Chichibabin's hydrocarbon, in accordance with its small diradical character (y₀=11.1 %) and large singlet–triplet gap (ΔE_S‐T=−10.8 kcal mol⁻¹). Variable‐temperature NMR studies on OxR‐2 disclose a slow cis/trans isomerization process in solution through a diradical transition state, with a moderate energy barrier (ΔG^≠_298K=15–16 kcal mol⁻¹). OxR‐3 exhibits a much larger diradical character (y₀=80.6 %) and a smaller singlet–triplet gap (ΔE_S‐T=−3.5 kcal mol⁻¹), and thus can be easily populated to paramagnetic triplet diradical. Our studies provide a new type of stable carbon‐centered monoradical and diradicaloid.     

Spectroscopic Observation of the Triplet Diradical State of a Cyclobutadiene

Tetrakis(trimethylsilyl)cyclobuta‐1,3‐diene ( 1 ) was subjected to a temperature‐dependent EPR study to allow the first spectroscopic observation of a triplet diradical state of a cyclobutadiene ( 2 ). From the temperature dependent EPR absorption area we derive a singlet→triplet ( 1 → 2 ) energy gap, E _ST, of 13.9 kcal mol⁻¹, in agreement with calculated values. The zero‐field splitting parameters D =0.171 cm⁻¹, E =0 cm⁻¹ are accurately reproduced by DFT calculations. The triplet diradical 2 is thermally accessible at moderate temperatures. It is not an intermediate in the thermal cycloreversion of cyclobutadiene to two acetylene molecules.     

Observation of a Thermally Accessible Triplet State Resulting from Rotation around a Main‐Group π Bond

We report the first direct spectroscopic observation by electron paramagnetic resonance (EPR) spectroscopy of a triplet diradical that is formed in a thermally induced rotation around a main‐group π bond, that is, the Si?Si double bond of tetrakis(di‐tert‐butylmethylsilyl)disilene ( 1 ). The highly twisted ground‐state geometry of singlet 1 allows access to the perpendicular triplet diradical 2 at moderate temperatures of 350–410 K. DFT‐calculated zero‐field splitting (ZFS) parameters of 2 accurately reproduce the experimentally observed half‐field transition. Experiment and theory suggest a thermal equilibrium between 1 and 2 with a very low singlet–triplet energy gap of only 7.3 kcal mol^?1.     

Quinoidal Azaacenes: 99 % Diradical Character

Quinoidal azaacenes with almost pure diradical character (y=0.95 to y=0.99) were synthesized. All compounds exhibit paramagnetic behavior investigated by EPR and NMR spectroscopy, and SQUID measurements, revealing thermally populated triplet states with an extremely low‐energy gap ΔE_ST′ of 0.58 to 1.0 kcal mol^?1. The species are persistent in solution (half‐life≈14–21 h) and in the solid state they are stable for weeks.     

Stable Expanded Porphycene‐Based Diradicaloid and Tetraradicaloid

The synthesis of a bithiophene‐bridged 34π conjugated aromatic expanded porphycene 1 and a cyclopentabithiophene bridged 32π conjugated anti‐aromatic expanded porphycene 2 by a McMurry coupling strategy is presented. Magnetic measurements and theoretical calculations reveal that both 1 and 2 exhibit an open‐shell singlet ground state with significant radical character (y₀=0.63 for 1 ; y₀=0.68, y₁=0.18 for 2 ; y₀: diradical character, y₁: tetraradical character) and a small singlet–triplet energy gap (ΔE_S‐T=?3.25 kcal mol^?1 for 1 and ΔE_S‐T=?0.92 kcal mol^?1 for 2 ). Despite the open‐shell radical character, both compounds display exceptional stability under ambient air and light conditions owing to effective delocalization of unpaired electrons in the extended cyclic π‐conjugation pathway.     

Nitrogen Analogues of o‐Quinodimethane with Unexpected non‐Kekulé Diradical Character

Two‐electron oxidations of three 1,2‐di(bisphenylamino)‐benzenes afforded a class of nitrogen analogues of o‐quinodimethane. Their electronic structures in the ground state were studied by spectroscopic techniques including EPR and UV‐vis absorption spectroscopy. They have open‐shell singlet ground states with thermally accessible triplet states. One of them ( 1 ²⁺) has been crystalized and isolated. SQUID measurements, single crystal X‐ray diffraction and theoretical calculations show 1 ²⁺ has unexpected non‐Kekulé diradical character, sharply different from o‐quinodimethane.     

Nitrogen Analogues of Thiele’s Hydrocarbon

A series of bis[N,N‐di‐(4‐methoxylphenyl)amino]arene dications 1 ²⁺– 3 ²⁺ have been synthesized and characterized. Their electronic structures were investigated by various experiments assisted by theoretical calculations. It was found that they are singlets in the ground state and that their diradical character is dependent on the bridging moiety. 3 ²⁺ has a smaller singlet–triplet energy gap and its excited triplet state is thermally readily accessible. The work provides a nitrogen analogue of Thiele’s hydrocarbon with considerable diradical character.     

An Unusually Small Singlet–Triplet Gap in a Quinoidal 1,6‐Methano[10]annulene Resulting from Baird’s 4n π‐Electron Triplet Stabilization

Within the continuum of π‐extended quinoidal electronic structures exist molecules that by design can support open‐shell diradical structures. The prevailing molecular design criteria for such structures involve proaromatic nature that evolves aromaticity in open‐shell diradical resonance structures. A new diradical species built upon a quinoidal methano[10]annulene unit is synthesized and spectroscopically evaluated. The requisite intersystem crossing in the open‐shell structure is accompanied by structural reorganization from a contorted Möbius aromatic‐like shape in S₀ to a more planar shape in the Hückel aromatic‐like T₁. This stability was attributed to Baird’s Rule which dictates the aromaticity of 4n π‐electron triplet excited states.     

Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals

Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔE_ST≈−64 cm⁻¹) and FM (ΔE_ST≥25 and 100 cm⁻¹) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.     

Toward Benzobis(thiadiazole)‐based Diradicaloids

We theoretically predicted that acetylene‐bridged benzo[1,2‐c ;4,5‐c ′]bis[1,2,5]thiadiazole (BBT) oligomers would show a quick increase of diradical character with the extension of chain length. To validate the hypothesis, six stable BBT‐based diradicaloids were synthesized and fully characterized by X‐ray crystallographic analysis and various spectroscopic measurements. Three of them showed prominent paramagnetic activity at elevated temperatures due to thermal population from the open‐shell singlet ground state to triplet excited state. It was also found that substitution by electron‐donating triphenylamine groups at the termini promoted the diradical character and reduced the singlet–triplet energy gap, and at the same time, resulted in intense near‐infrared absorption.     

Intramolecular [2+2] Photocycloaddition of 3‐ and 4‐(But‐3‐enyl)oxyquinolones: Influence of the Alkene Substitution Pattern,Photophysical Studies,and Enantioselective Catalysis by a Chiral Sensitizer

The intramolecular [2+2] photocycloaddition of four 4‐(but‐3‐enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH₂, Z‐CHEt, E‐CHEt, CMe₂) and two 3‐(but‐3‐enyl)oxyquinolones (substitution pattern: CH₂, CMe₂) was studied. Upon direct irradiation at λ=300 nm, the respective cyclobutane products were formed in high yields (83–95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z‐ or E‐substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio‐ and diastereomers with almost identical composition. The mechanistic course of the photocycloaddition was elucidated by transient absorption spectroscopy. A triplet intermediate was detected for the title compounds, which–in contrast to simple alkoxyquinolones such as 3‐butyloxyquinolone and 4‐methoxyquinolone–decayed rapidly (τ≈1 ns) through cyclization to a triplet 1,4‐diradical. The diradical can evolve through two reaction channels, one leading to the photoproduct and the other leading back to the starting material. When the photocycloaddition was performed in the presence of a chiral sensitizer (10 mol %) upon irradiation at λ=366 nm in trifluorotoluene as the solvent, moderate to high enantioselectivities were achieved. The two 3‐(but‐3‐enyl)oxyquinolones gave enantiomeric excesses (ees) of 60 and 64 % at ?25 °C, presumably because a significant racemic background reaction occurred. The 4‐substituted quinolones showed higher enantioselectivities (92–96 % ee at ?25 °C) and, for the terminally Z‐ and E‐substituted substrates, an improved regio‐ and diastereoselectivity.     

Modulation of Thermally Activated Delayed Fluorescence in Waterborne Polyurethanes via Charge‐Transfer Effect

Here, we designed several waterborne polyurethanes (WPUs) with efficient thermally activated delayed fluorescence (TADF) via serving charge‐transfer (CT) states as a mediate bridge between singlet and triplet states to boost reverse intersystem crossing (RISC). By tuning substituents of diphenyl sulfone (DS), we found that O,O′‐ and S,S′‐substituted DS covalently incorporated in WPUs solely show typical fluorescence emission with lifetimes in the nanosecond range. Interestingly, TADF appears by replacing the substituent with the nitrogen atom, of which lifetimes are up to ≈10 microseconds and ≈1 millisecond in air and vacuum, respectively, even though the energy gap between singlet and triplet states (ΔE_ST) is still large for generating TADF. To explain this phenomenon, an energy level mode based on CT states and an ³(n‐π*) receiver state was proposed. By the rational modulation of CT states, it is possible to tune the ΔE_ST to render TADF‐based materials suitable for versatile applications.     

Crystalline Diradical Dianions of Pyrene‐Fused Azaacenes

Although diradicals and azaacenes have been greatly attractive in fundamental chemistry and functional materials, the isolable diradical dianions of azaacenes are still unknown. Herein, we describe the first isolation of pyrene‐fused azaacene diradical dianion salts [(18‐c‐6)K(THF)₂]⁺[(18‐c‐6)K]⁺? 1 ^2?.. and [(18‐c‐6)K(THF)]²⁺? 2 ^2?.. by reduction of the neutral pyrene‐fused azaacene derivatives 1 and 2 with excess potassium graphite in THF in the presence of 18‐crown‐6. Their electronic structures were investigated by various experiments, in conjunction with theoretical calculations. It was found that both dianions are open‐shell singlets in the ground state and their triplet states are thermally readily accessible owing to the small singlet–triplet energy gap. This work provides the first examples of crystalline diradical dianions of azaacenes with considerable diradical character.     

The Triplet State of 6‐thio‐2′‐deoxyguanosine: Intrinsic Properties and Reactivity Toward Molecular Oxygen

Thiopurine prodrugs are currently among the leading treatment options for leukemia, immunosuppression, and arthritis. Patients undergoing long‐term thiopurine treatment are at a higher risk of developing sunlight‐induced skin cancers than the general population. This side effect originates from the cellular metabolization of thiopurine prodrugs to form 6‐thio‐2′‐deoxyguanosine, which can absorb UVA radiation, populating its reactive triplet state and leading to oxidatively generated damage. However, the photo‐oxidation mechanism is not fully understood. In this contribution, the oxidation potential and the adiabatic triplet energy of 6‐thio‐2′‐deoxyguanosine are estimated computationally, whereas the intrinsic rate of triple‐state decay and the rate constant for triplet quenching by molecular oxygen are determined using time‐resolved spectroscopic techniques. A singlet oxygen quantum yield of 0.24 ± 0.02 is measured in aqueous solution (0.29 ± 0.02 in acetonitrile). Its magnitude correlates with the relatively low percentage of triplet‐O₂ collision events that generate singlet oxygen (S_Δ = 37%). This behavior is rationalized as being due to the exergonic driving force for electron transfer between the triplet state of 6‐thio‐2′‐deoxyguanosine and molecular oxygen (ΔG_ET = ?69.7 kJ mol^?1), resulting in the formation of a charge‐transfer complex that favors nonradiative decay to the ground state over triplet energy transfer.     

1‐[(E)‐2‐Arylethenyl]‐2,2‐diphenylcyclopropanes: Kinetics and Mechanism of Rearrangement to Cyclopentenes

Kinetic measurements for the thermal rearrangement of 2,2‐diphenyl‐1‐[(E)‐styryl]cyclopropane ( 22a ) to 3,4,4‐triphenylcyclopent‐1‐ene ( 23a ) in decalin furnished ΔH =31.0±1.2 kcal mol^?1 and ΔS =?6.0±2.6 e.u. The lowering of ΔH^≠ by 20 kcal mol^?1, compared with the rearrangement of the vinylcyclopropane parent, is ascribed to the stabilization of a transition structure (TS) with allylic diradical character. The racemization of (+)‐(S)‐ 22a proceeds with ΔH =28.2±0.8 kcal mol^?1 and ΔS =?5±2 e.u., and is at 150° 106 times faster than the rearrangement. Seven further 1‐(2‐arylethenyl)‐2,2‐diphenylcyclopropanes 22 , (E)‐ and (Z)‐isomers, were synthesized and characterized. The (E)‐compounds showed only modest substituent influence in their k_rac (at 119.4°) and k_isom (at 159.3°) values. The lack of solvent dependence of rate opposes charge separation in the TS, but a linear relation of log k_rac with log p.r.f., i.e., partial rate factors of radical phenylations of ArH, agrees with a diradical TS. The ring‐opening of the preponderant s‐trans‐conformation of 22 gives rise to the 1‐exo‐phenylallyl radical 26 that bears the diphenylethyl radical in 3‐exo‐position, and is responsible for racemization. The 1‐exo‐3‐endo‐substituted allylic diradical 27 arises from the minor s‐gauche‐conformation of 22 and is capable of closing the three‐ or the five‐membered ring, 22 or 23 , respectively. The discussion centers on the question whether the allylic diradical is an intermediate or merely a TS. Quantum‐chemical calculations by Houk et al. (1997) for the parent vinylcyclopropane reveal the lack of an intermediate. Can the conjugation of the allylic diradical with three Ph groups carve the well of an intermediate?     

Molecular Design of Highly Efficient Heavy‐Atom‐Free Triplet BODIPY Derivatives for Photodynamic Therapy and Bioimaging

Novel BODIPY photosensitizers were developed for imaging‐guided photodynamic therapy. The introduction of a strong electron donor to the BODIPY core through a phenyl linker combined with the twisted arrangement between the donor and the BODIPY acceptor is essential for reducing the energy gap between the lowest singlet excited state and the lowest triplet state (ΔE_ST), leading to a significant enhancement in the intersystem crossing (ISC) of the BODIPYs. Remarkably, the BDP‐5 with the smallest ΔE_ST (ca. 0.44 eV) exhibited excellent singlet oxygen generation capabilities in both organic and aqueous solutions. BDP‐5 also displayed bright emission in the far‐red/near‐infrared region in the condensed states. More importantly, both in vitro and in vivo studies demonstrated that BDP‐5 NPs displayed a high potential for photodynamic cancer therapy and bioimaging.     

Conformationally Flexible Bis(9‐fluorenylidene)porphyrin Diradicaloids

A stable 5,10‐bis(9‐fluorenylidene)porphyrin (Por‐Fl) diradicaloid was synthesized. It shows a quinoidal, saddle‐shaped geometry in the single crystal but can be thermally populated to a triplet diradical both in solution and in the solid state. Coordination with the Ni²⁺ ion (Por‐Fl‐Ni) does not significantly change the contorted conformation but reduces the singlet–triplet gap. Heat‐induced geometric change can explain the observed paramagnetic properties as well as unusual hysteresis in SQUID measurements. On the other hand, protonation (Por‐Fl‐2H⁺) dramatically changes the conformation while maintains the closed‐shell electronic structure. Our studies demonstrate how heat, coordination, and protonation affect the geometry, diradical character, and physical properties of conformationally flexible open‐shell singlet diradicaloids.