Stable Dication Research Articles

Linear Non-benzenoid Isomer of Acene Fusing Chrysene with Azulene Units.

Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have received considerable attention owing to their distinctive optical and electrical properties. Nevertheless, the synthesis and optoelectronic application of non-benzenoid PAHs remain challenging. Herein, we present a facile synthesis of linear non-benzenoid PAH with an armchair edge, diACh, by fusing chrysene with two azulene units. We systematically investigated the optical and electrical properties, which were also compared to its isomers, including benzenoid and non-benzenoid zigzag edge isomers. diACh exhibits global aromaticity, good planarity, and suitable highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels. The protonation of diACh in solution successively forms a stable tropylium cation and dication. Moreover, the neutral, cationic, and dicationic states of diACh can be transformed with remarkable reversibility during the protonation-deprotonation process, as confirmed by ultraviolet-visible absorptions, fluorescence spectra, 1H nuclear magnetic resonance, and theoretical calculations. Additionally, we fabricate p-type organic field-effect transistor (OFET) devices based on diACh with hole mobility up to 0.026 cm2 V-1 s-1, and we further develop OFET-based acid vapor sensors with good sensitivity, recyclability, and selectivity. These findings underscore the unique properties of linear non-benzenoid PAHs with an armchair edge engendered by the fusion of azulene with the acene backbone, showcasing prospective applications in organic optoelectronics.

Highly Sensitive, Easy-to-Use, One-Step Detection of Peroxide-, Nitrate- and Chlorate-Based Explosives with Electron-Rich Ni Porphyrins.

Homemade explosives, such as peroxides, nitrates, and chlorates, are increasingly abused by terrorists, criminals, and amateur chemists. The starting materials are easily accessible and instructions on how to make the explosives are described on the Internet. Safety considerations raise the need to detect these substances quickly and in low concentrations using simple methods. Conventional methods for the detection of these substances require sophisticated, electrically operated, analytical equipment. The simpler chemical detection methods are multistep and require several chemicals. We have developed a simple, one-step method that works similarly to a pH test strip in terms of handling. The analytical reaction is based on an acid-catalyzed oxidation of an electron-rich porphyrin to an unusually stable radical cation and dication. The detection limit for the peroxide-based explosive triacetone triperoxide (TATP), which is very frequently used by terrorists, is 40 ng and thus low enough to detect the substance without direct contact via the gas phase. It is sufficient to bring the stick close to the substance to observe a color change from red to green. Nitrates and chlorates, such as ammonium nitrate, urea nitrate, or potassium chlorate, are detected by direct contact with a sensitivity of 85-350 ng. A color change from red to dark brown is observed. The test thus detects all homemade explosives and distinguishes between the extremely impact-, shock-, and friction-sensitive peroxides and the less sensitive nitrates and chlorates by color change of a simple test strip.

A Novel Bisquaternary Ammonium Compound as an Anion Sensor-ESI-MS and Fluorescence Study.

Electrospray ionization mass spectrometry (ESI-MS) analysis is frequently associated with noncovalent adduct formation, both in positive and negative modes. Anion binding and sensing by mass spectrometry, notably more challenging compared to cation binding, will have major research potential with the development of appropriate sensors. Here, we demonstrated identification of stable bisquaternary dication adducts with trifluoroacetate (TFA-), Cl- and HSO4- in positive-mode ESI-MS analysis. The observed adducts were stable in MS/MS mode, leading to the formation of characteristic fragment ions containing a covalently bound anion, which requires bond reorganization. This phenomenon was confirmed by computational methods. Furthermore, given that anion detection and anion sensor chemistry have gained significant prominence in chemistry, we conducted an analysis of the fluorescent properties of bisquaternary ammonium compound as a potential anion sensor.

Synthese und Charakterisierung eines stabilen Nickelocenium‐Dikation‐Salzes

AbstractWir berichten über die Synthese und Charakterisierung der Nickelocenium‐Kationen [NiCp2]⋅+ und [NiCp2]2+ als deren [F‐{Al(ORF)3}2]− (Cp = C5H5; RF=C(CF3)3) Salze. Das diamagnetische [NiCp2]2+ ist das erste Beispiel für die Isolierung eines unsubstituierten Metallocen Dikations. Beide Salze wurden durch Reaktion von neutralem NiCp2 mit [NO]+[F‐{Al(ORF)3}2]− in 1,2,3,4‐Tetrafluorbenzol (4FB) erzeugt. Die Salze konnten durch Einkristall‐Röntgenbeugung charakterisiert werden, wobei kürzere Metall‐Ligand‐Bindungslängen für das höher geladene Salz gemessen wurden. Pulver‐Röntgenbeugung zeigte, dass die Salze phasenrein erhalten wurden. Cyclovoltammetrie in 4FB ergab quasi‐reversibel Redoxwellen bei −0.44 (0→1) und +1.17 V (1→2) gegen Fc/Fc+. Das 1H NMR von [NiCp2]2+ weist ein Singulett bei 8.6 ppm auf, während das paramagnetische [NiCp2]⋅+ deutlich Hochfeld auf −103.1 ppm verschoben ist.

Synthesis and Characterization of a Stable Nickelocenium Dication Salt.

We report the synthesis and characterization of the nickelocenium cations [NiCp2 ]⋅+ and [NiCp2 ]2+ as their [F-{Al(ORF )3 }2 ]- (Cp = C5 H5 ; RF =C(CF3 )3 ) salts. Diamagnetic [NiCp2 ]2+ represents the first example for the isolation of an unsubstituted parent metallocene dication. Both salts were generated by reacting neutral NiCp2 with [NO]+ [F-{Al(ORF )3 }2 ]- in 1,2,3,4-tetrafluorobenzene (4FB). The salts were characterized by single crystal X-ray diffraction (XRD), indicating shorter metal-ligand bond lengths for the higher charged salt. Powder XRD shows the salts to be phase pure, cyclic voltammetry in 4FB gave quasi reversible redox waves at -0.44 (0→1) and +1.17 V (1→2) vs Fc/Fc+ . The 1 H NMR of [NiCp2 ]2+ is a singlet at 8.6 ppm, whereas paramagnetic [NiCp2 ]⋅+ is significantly shifted upfield to -103.1 ppm.

Stable Dication Diradicals of Triply Fused Metallo Chlorin-Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity.

We report an unexpected rearrangement, controlled by the nature of the bridge, leading to the formation of novel, remarkably stable triply fused dinickel(II)/dicopper(II) chlorin-porphyrin dication diradical heterodimers in excellent yields. Here, a dipyrromethene bridge gets completely fused between two porphyrin macrocycles with two new C-C and one C-N bonds. The two macrocycles exhibit extensive π-conjugation through the bridge, which results in an antiferromagnetic coupling between the two π-cation radicals. In addition, the macrocyclic distortion also favours a rare intramolecular ferromagnetic interaction between the CuII and π-cation radical spins to form a triplet state. The structural and electronic perturbation in the unconjugated dication diradical possibly enables the bridging pyrrolic nitrogen to undergo a nucleophilic attack at the nearby β-carbon of the porphyrin π-cation radical with a computed free energy barrier of >20 kcal mol-1 which was supplied in the form of reflux condition to initiate such a rearrangement process. UV-vis, EPR and ESI-MS spectroscopies were used to monitor the rearrangement process in situ in order to identify the key reactive intermediates leading to such an unusual transformation.

Electronic states, spectroscopic properties, electronic transitions, and bonding in ScH2+: A thermodynamic stable transition metal-hydrogen dication

Eight bound singlet and triplet electronic states of the diatomic dication ScH2+ are characterized theoretically at the SA-CASSCF/icMRCI/aug-cc-pV5Z level of theory by the construction of potential energy curves, and the evaluation of spectroscopic parameters. The states dissociating into the first channel are all thermodynamically stable. For the ground state, covalent bonding plays a relevant role in the stabilization of the molecule; for the other states, bonding results mainly from electrostatic charge-induced dipole interaction. Dipole moment (relative to the center of mass) functions and vibrationally averaged dipole moments quantify the polarity of the molecule. After evaluating transition moment functions, transition probabilities for spontaneous emission for selected pair of states are estimated by the Einstein Av´,v´´ coefficients and the stronger transitions identified; radiative lifetimes are also reported. Not yet known experimentally, this work is expected to motivate experimental investigations of transition metal-monohydrides diatomic dications.

Head-to-Tail Dimerization of N-Heterocyclic Diazoolefins.

The head-to-tail dimerization of N-heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins.

Head‐to‐Tail Dimerization of N‐Heterocyclic Diazoolefins

AbstractThe head‐to‐tail dimerization of N‐heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins.

Synthesis and structural evaluation of closed-shell folded and open-shell twisted hexabenzo[5.6.7]quinarene.

We describe the synthesis and characterization of hexabenzo[5.6.7]quinarene, which is composed of an anthraquinodimethane (AQD) central core that is end-capped with fluorenyl and dibenzosuberenyl groups. Due to strong intramolecular spin-spin interaction through the central AQD unit, this compound is obtained as a stable folded form. Isolation of the stable twisted dication by oxidation and reduction of the dication yields a twisted triplet species, which thermally reverts to the folded form. This is a spin-switching system based on a combination of chemical oxidation/reduction and thermal stimulation.

Stable excited dication: trapping on the S1 state of formaldehyde dication after strong field ionization.

Combined theoretical and experimental work examines the dynamics of dication formaldehyde produced by strong field ionization. Trajectory surface hopping dynamics on the first several singlet electronic states of the formaldehyde dication are used to examine the relaxation pathways and dissociation channels, while kinetic energy distributions after strong field ionization of formaldehyde and deuterated formaldehyde are used to confirm the theoretical predictions. We find that the first excited state of the formaldehyde dication is stable, neither decays to the ground state nor dissociates, even though the ground state and higher lying states are directly dissociative. The stability of the first excited state is explained by its symmetry which does not allow for radiative or nonradiative transitions to the ground state and by large barriers to dissociate on the excited state surface.

Electrosynthesis of electrochromic polymers based on bis-(4-(N-carbazolyl)phenyl)-phenylphosphine oxide and 3,4-propylenedioxythiophene derivatives and studies of their applications in high contrast dual type electrochromic devices

Five phenylphosphine oxide-containing polymers (PBCPO (poly(bis-(4-(N-carbazolyl)phenyl)-phenylphosphine oxide)), P(BCPO-co-ProD-Me2), P(BCPO-co-ProD-Et2), P(BCPO-co-ProD-Bz2), and P(BCPO-co-ProD)) are electrodeposited on indium tin oxide (ITO) coated glass slide and their electrochromic performances are characterized. The optical band gap of PBCPO is 3.14 eV. P(BCPO-co-ProD-Bz2) attains a high transmittance change (ΔT = 55% at 740 nm) and shows multicolored electrochromism from light tan (0.0 V), grayish-green (0.4 V), greenish-gray (1.1 V) to deep gray (1.2 V). Electrochromic devices (ECDs) containing phenylphosphine oxide-based polycarbazoles and poly(3,4-ethylenedioxythiophene) (PEDOT) as active electrode layers are constructed. PBCPO/PEDOT ECD displays light gray, gray, and greenish-gray at 0.0, 0.8, and 1.9 V, respectively. P(BCPO-co-ProD-Bz2)/PEDOT ECD displays a high optical contrast (ΔT = 42.5% at 630 nm) and P(BCPO-co-ProD)/PEDOT ECD shows a high coloration efficiency (η = 454.1 cm2•C−1 at 630 nm). In addition, P(BCPO-co-ProD derivatives)/PEDOT ECDs have adequate optical memories and long-term redox cyclic stability.Background: Polycarbazoles can create considerably stable radical cations (polarons) and dications (bipolarons) when increasing potentials or doping chemicals. Moreover, carbazole and phenylphosphine oxide are donor (D) and acceptor (A) units in BCPO, respectively. The incorporation of phenylphosphine oxide in polycarbazoles gives rise to the improvement of charge balances and carrier mobilities. It is interesting to investigate the absorption spectra and multicolored electrochromisms of five phenylphosphine oxide-containing polycarbazoles and their corresponding ECDs upon undergoing a redox process.Methods: A series of phenylphosphine oxide-containing anodic polymers (PBCPO, P(BCPO-co-ProD-Me2), P(BCPO-co-ProD-Et2), P(BCPO-co-ProD-Bz2), and P(BCPO-co-ProD)) are electrodeposited on ITO coated glass. The absorption spectra, color variations, response time, and long-term electrochemical stability of PBCPO/PEDOT, P(BCPO-co-ProD-Me2)/PEDOT, P(BCPO-co-ProD-Et2)/PEDOT, P(BCPO-co-ProD-Bz2)/PEDOT, and P(BCPO-co-ProD)/PEDOT ECDs are investigated comprehensively.Significant findings: The as-prepared phenylphosphine oxide-containing polycarbazoles exhibit multicolored electrochromism and high transmittance change (ΔT = 55% at 740 nm), which provide new structural insights to develop new generation electrochromic electrodes.

One- and Two-Electron Transfer Oxidation of 1,4-Disilabenzene with Formation of Stable Radical Cations and Dications.

Electron‐transferable oxidants such as B(C6F5)3/nBuLi, B(C6F5)3/LiB(C6F5)4, B(C6F5)3/LiHBEt3, Al(C6F5)3/(o‐RC6H4)AlH2 (R=N(CMe2CH2)2CH2), B(C6F5)3/AlEt3, Al(C6F5)3, Al(C6F5)3/nBuLi, Al(C6F5)3/AlMe3, (CuC6F5)4, and Ag2SO4, respectively were employed for reactions with (L)2Si2C4(SiMe3)2(C2SiMe3)2 (L=PhC(NtBu)2, 1). The stable radical cation [1]+. was formed and paired with the anions [nBuB(C6F5)3]− (in 2), [B(C6F5)4]− (in 3), [HB(C6F5)3]− (in 4), [EtB(C6F5)3]− (in 5), {[(C6F5)3Al]2(μ‐F)]− (in 6), [nBuAl(C6F5)3]− (in 7), and [Cu(C6F5)2]− (in 8), respectively. The stable dication [1]2+ was also generated with the anions [EtB(C6F5)3]− (9) and [MeAl(C6F5)3]− (10), respectively. In addition, the neutral compound [(L)2Si2C4(SiMe3)2(C2SiMe3)2][μ‐O2S(O)2] (11) was obtained. Compounds 2–11 are characterized by UV‐vis absorption spectroscopy, X‐ray crystallography, and elemental analysis. Compounds 2–8 are analyzed by EPR spectroscopy and compounds 9–11 by NMR spectroscopy. The structure features are discussed on the central Si2C4‐rings of 1, [1]+., [1]2+, and 11, respectively.

Synthesis, Properties, and Packing Structures of Wing-Shaped N-Doped Nanographene in Various Oxidation States.

A rigid wing-shaped bicyclo[2.2.2]octadiene-fused bis-hexapyrrolohexaazacoronene (HPHAC) is synthesized, and subsequent chemical oxidation affords a stable biradical dication and an aromatic tetracation. The physicochemical properties and single-crystal structures in various oxidation states are characterized. The face-to-face π-stacked dimeric structures are observed in the neutral and dicationic states. The HPHAC flakes can act as aromatic walls in a tetracation state, producing enlarged induced magnetic shielding space through the superimposition effect.

Electrophotocatalytic diamination of vicinal C-H bonds.

The conversion of unactivated carbon-hydrogen (C-H) bonds to carbon-nitrogen (C-N) bonds is a highly valued transformation. Existing strategies typically accomplish such reactions at only a single C-H site because the first derivatization diminishes the reactivity of surrounding C-H bonds. Here, we show that alkylated arenes can undergo vicinal C-H diamination reactions to form 1,2-diamine derivatives through an electrophotocatalytic strategy, using acetonitrile as both solvent and nitrogen source. The reaction is catalyzed by a trisaminocyclopropenium (TAC) ion, which undergoes anodic oxidation to furnish a stable radical dication while the cathodic reaction reduces protons to molecular hydrogen. Irradiation of the TAC radical dication (wavelength of maximum absorption of 450 to 550 nanometers) with a white-light compact fluorescent light generates a strongly oxidizing photoexcited intermediate. Depending on the electrolyte used, either 3,4-dihydroimidazole or aziridine products are obtained.

Stable Radical Cation and Dication of a 1,4-Disilabenzene.

The reaction of (LSi:)2 (1; L = PhC(NtBu)2) with 2 equiv of Me3SiC2C2SiMe3 resulted in the formation of (Me3SiC2)2(Me3Si)2C4Si2(L)2 (2). 2 exhibited a one-electron transfer when treated with 1 equiv of [Ph3C]+[B(C6F5)4]- to yield [(Me3SiC2)2(Me3Si)2C4Si2(L)2]·+[B(C6F5)4]- (3) and Ph3CCPh3, respectively. When compound 2 was treated with 2 equiv of AgOSO2CF3 a transfer of two electrons occurred to produce [(Me3SiC2)2(Me3Si)2C4Si2(L)2]2+·2[OSO2CF3]- (4) and elemental silver. The 1,4-disilabenzene 2 is disclosed of an open-shell singlet diradical character, and 3 and 4 are, respectively, the elusive stable radical cation and dication species of the 1,4-disilabenzene (2). Furthermore, 2 reacted with group 16 elements of O, S, and Se by oxidative addition to form (Me3SiC2)2(Me3Si)2C4Si2(L)2(μ-O2) (5) and (Me3SiC2)2(Me3Si)2C4Si2(L)2(μ-E) (E = S (6) and Se (7)), respectively.

Spectroscopic characterization of a thermodynamically stable doubly charged diatomic molecule: MgAr2.

Although numerous doubly positively charged diatomic molecules (diatomic dications) are known from investigations using mass spectrometry and ab initio quantum chemistry, only three of them, NO2+, N22+ and DCl2+, have been studied using rotationally resolved optical spectroscopy and only about a dozen by vibrationally resolved double-ionization methods. So far, no thermodynamically stable diatomic dication has been characterized spectroscopically, primarily because of experimental difficulties associated with their synthesis in sufficient densities in the gas phase. Indeed, such molecules typically involve, as constituents, rare-gas, halogen, chalcogen, and metal atoms. We report here on a new approach to characterize molecular dications based on high-resolution photoelectron spectroscopy of the singly charged parent molecular cation and present the first spectroscopic characterization of a thermodynamically stable diatomic dication, MgAr2+. From the fully resolved vibrational and partially resolved rotational structures of the photoelectron spectra of 24MgAr+ and 26MgAr+, we determined the potential-energy function of the electronic ground state of MgAr2+, its dissociation (binding) energy (D0 = 10 690(3) cm−1), and its harmonic (ωe(24MgAr2+) = 327.02(11) cm−1) and anharmonic (ωexe(24MgAr2+) = 2.477(15) cm−1) vibrational constants. The analysis enables us to explain quantitatively how the strong bond arises in this dication despite the fact that Ar and Mg2+ both have a full-shell rare-gas electronic configuration.

Electrochemical Polymerization of Pyrrole–Perimidine Hybrids: Low-Band-Gap Materials with High n-Doping Activity

Conductive π-conjugated polymers were electrochemically generated from a variety of donor–acceptor pyrroles containing fused perimidine subunits. Alternating oxidative and reductive polarization of these precursors induces multidirectional coupling involving both perimidine and acenaphtho[1,2-c]pyrrole moieties, producing cross-linked polymeric structures. Chemical oxidation experiments and computational analyses of spin densities in the charged pyrrole intermediates indicate that the formation of inter-perimidine linkages occurs prior to pyrrole–pyrrole couplings. In the resulting polymers, a very stable dication state is achievable with the positive charge located on the bis-perimidine linker. These polymers do not show any stable neutral state and can be easily reduced. Cationic and anionic states of these electrogenerated films were investigated in the solid state by UV–vis–NIR and EPR spectroelectrochemistry, assisted by DFT calculations.

Stable Radical Cation and Dication of an N-Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity.

One- and two-electron oxidation of a digallene stabilized by an N-heterocyclic carbene afforded the first stable gallium-based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu3 SnH and cyclo-S8 was studied; a digallium-hydride cation salt containing a Ga-Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder-like Ga4 S4 core structure were obtained, respectively.

Stable Radical Cation and Dication of an N‐Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity

AbstractOne‐ and two‐electron oxidation of a digallene stabilized by an N‐heterocyclic carbene afforded the first stable gallium‐based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu3SnH and cyclo‐S8 was studied; a digallium–hydride cation salt containing a Ga−Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder‐like Ga4S4 core structure were obtained, respectively.