Facile Energy Release from Substituted Dewar Isomers of 1,2­Dihydro-1,2­azaborinines Catalyzed by Coinage Metal Lewis Acids.

Molecular solar thermal systems (MOST) represent an auspicious solution for the storage of solar energy. We report silver salts as a unique class of catalysts, capable of releasing the stored energy from the promising 1,2-dihydro-1,2-azaborinine based MOST system. Mechanistic investigations provided insights into the silver catalyzed thermal backreaction, concurrently unveiling the first crystal structure of a 2-aza-3-borabicyclo[2.2.0]hex-5-ene, the Dewar isomer of 1,2-dihydro-1,2-azaborinine. Quantification of activation energies by kinetic experiments has elucidated the advantageous energy outcomes associated with Lewis acid catalysts, a phenomenon corroborated through computational analysis. By means of low temperature NMR spectroscopy, mechanistic insights into the coordination of Ag+ to the 1,2-dihydro-1,2-azaborinine were gained.

Gas Phase Ionization Energy of Heptacene.

The ionization energy is a fundamental property that is relevant to charge transport in organic semiconductors. We report adiabatic ionization energies (AIEs) of heptacene at 6.21 and 7.20 eV for the X̃+B2g and Ã+Au states, respectively, as the next larger member of the acene series using mass- and isomer-selective double imaging photoelectron photoion coincidence spectroscopy. The X̃+ state energy decreases monotonically with an increase in size within the homologous series of acenes and approaches an asymptotic limit [AIE(polyacene) = 5.94 ± 0.06 eV] based on a fit with an exponential decay function. As byproducts of heptacene formation from cycloreversion of diheptacenes, 5,18-, 7,16-, and 6,17-dihydroheptacene can be detected, and their AIE is similar to that of their largest acene subunit (anthracene and tetracene, respectively), in very good agreement with computational treatments.

Strain induced reactivity of cyclic iminoboranes: the (2 + 2) cycloaddition of a 1H-1,3,2-diazaborepine with ethene.

Iminoboranes have gathered immense attention due to their reactivity and potential applications as isoelectronic and isosteric alkynes. While cyclic alkynes are well investigated and useful reagents, cyclic iminoboranes are underexplored and their existence was inferred only via trapping experiments. We report the first direct spectroscopic evidence of a cyclic seven-membered iminoborane, 1-(tert-butyldimethylsilyl)-1H-1,3,2-diazaborepine 2, under cryogenic matrix isolation conditions. The amino-iminoborane 2 was photochemically generated in solid argon at 4 K from 2-azido-1-(tert-butyldimethylsilyl)-1,2-dihydro-1,2-azaborinine (3) and was characterized using FT-IR, UV-vis spectroscopy, and computational chemistry. The characteristic BN stretching vibration (1751 cm-1) is shifted by about 240 cm-1 compared to linear amino-iminoboranes indicating a significant weakening of the bond. The Lewis acidity value determined computationally (LAB = 9.1 ± 2.6) is similar to that of boron trichloride, and twelve orders of magnitude lower than that of 1,2-azaborinine (BN-aryne, LAB = 21.5 ± 2.6), a six-membered cyclic iminoborane. In contrast to the latter, the reduced ring strain of 2 precludes nitrogen fixation, but it unexpectedly allows facile (2 + 2) cycloaddition reaction with C2H4 under matrix isolation conditions at 30 K.

Optical Absorption Properties in Pentacene/Tetracene Solid Solutions.

Modifying the optical and electronic properties of crystalline organic thin films is of great interest for improving the performance of modern organic semiconductor devices. Therein, the statistical mixing of molecules to form a solid solution provides an opportunity to fine-tune optical and electronic properties. Unfortunately, the diversity of intermolecular interactions renders mixed organic crystals highly complex, and a holistic picture is still lacking. Here, we report a study of the optical absorption properties in solid solutions of pentacene and tetracene, two prototypical organic semiconductors. In the mixtures, the optical properties can be continuously modified by statistical mixing at the molecular level. Comparison with time-dependent density functional theory calculations on occupationally disordered clusters unravels the electronic origin of the low energy optical transitions. The disorder partially relaxes the selection rules, leading to additional optical transitions that manifest as optical broadening. Furthermore, the contribution of diabatic charge-transfer states is modified in the mixtures, reducing the observed splitting in the 0-0 vibronic transition. Additional comparisons with other blended systems generalize our results and indicate that changes in the polarizability of the molecular environment in organic thin-film blends induce shifts in the absorption spectrum.

Synthesis of Tridecacene by Multistep Single-Molecule Manipulation.

Acenes represent a unique class of polycyclic aromatic hydrocarbons that have fascinated chemists and physicists due to their exceptional potential for use in organic electronics. While recent advances in on-surface synthesis have resulted in higher acenes up to dodecacene, a comprehensive understanding of their fundamental properties necessitates their expansion toward even longer homologues. Here, we demonstrate the on-surface synthesis of tridecacene via atom-manipulation-induced conformational preparation and dissociation of a trietheno-bridged precursor on a Au(111) surface. The generated tridecacene has been investigated by scanning tunneling microscopy and spectroscopy (STM/STS), combined with first-principles calculations. We observe that the STS transport gap (1.09 eV) shrinks again following the gap reopening of dodecacene (1.4 eV). Spin-polarized density functional theory calculations confirm an antiferromagnetic open-shell ground-state electronic configuration for tridecacene in the gas phase. Interestingly, tridecacene's open-shell character is significantly reduced upon interaction with the Au(111) surface despite being only physisorbed. The interaction with the surface leads to a lowering of the magnetization of tridecacene, a reduced gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), compared to the gas phase, and a reduced relative energy to the nonmagnetic state, making it nearly isoenergetic. These observations show qualitatively that the influence of the Au(111) substrate on the properties of long acenes is significant, which is important for interpreting the measured STS transport gaps. Our work contributes to a fundamental understanding of the electronic properties of long acenes, confirming a nonmonotonous length-dependent HOMO-LUMO gap, and to the development of multistep tip-assisted synthesis of elusive compounds.

Direct Spectroscopic Identification of BN-Arynes and Subtle Steric Effects on Nitrogen Fixation.

1,2-Azaborinines are the BN analogues of arynes through exchange of the formal CC triple bond by an isoelectronic BN bond. The BN-arynes are an underexplored class of reactive intermediates. Dibenzo[c,e][1,2]azaborinine (10,9-BN-phenanthryne) 1 was inferred as reactive intermediate by trapping reactions. Here it is shown that 1 can be generated in the gas phase by thermolysis from the pyridine adduct of 9-azido-9-borafluorene by cleavage of the dative bond with pyridine and dinitrogen extrusion. The ionization potential of 1 is 8.2 eV with ionization resulting from the π HOMO. Under cryogenic matrix isolation conditions, 9-azido-9-borafluorene photolysis results in isomerization to the dinitrogen adduct of 1 without involvement of a triplet borylnitrene intermediate. Photochemical nitrogen extrusion from 1 ⋅ N2 is not possible and nitrogen fixation is irreversible under cryogenic conditions. In contrast, 2,4,7,9-tetra-tert-butyldibenzo[c,e][1,2]azaborinine can be photogenerated from the corresponding azidoborole precursor under cryogenic matrix isolation conditions, and nitrogen fixation is precluded due to steric hindrance. The BN stretching vibration at about 1750 cm-1 is much weaker than in typical linear diaryl iminoboranes.

Accessing unusual heterocycles: ring expansion of benzoborirenes by formal cycloaddition reactions.

Benzoborirenes are a very rare class of strained boron heterobicyclic systems. In this study a kinetically stabilized benzoborirene 1 is shown to react with multiple bonds of trimethylphosphine oxide, acetaldehyde, and tert-butyl isonitrile. The (2 + 2) cycloaddition product with trimethylphosphine oxide, benzo[c][1,2,5]oxaphosphaborole, has a long apical PO bond (194.0 pm) that must be considered on the border line between ionic and covalent according to the natural bond orbital, quantum theory of atoms in molecules, and compliance matrix approaches to the description of chemical bonding. The coordination compound between the benzoborirene and phosphine oxide was observed by NMR spectroscopy at 213 K. The Lewis acidity of 1 is similar to that of B(OCH2CF3)3 and B(C6F5)3 based on the 31P{1H} NMR chemical shift of the Lewis acid base complexes with trimethylphosphine oxide at 213 K. Benzoboriene 1 does not react with acetone, but forms a (2 + 2) cycloaddition product, an oxaborole, with acetaldehyde. In contrast, it undergoes a double (2 + 1) reaction with tert-butyl isonitrile to yield a boro-indane derivative under mild conditions. The observed reactivity of 1 is in agreement with computational analyses of the respective potential energy surfaces.

Orientation, electronic decoupling and band dispersion of heptacene on modified and nanopatterned copper surfaces.

The adsorption of heptacene (7 A) on Cu(110) and Cu(110)-(2 × 1)-O was studied with scanning tunneling microscopy, photoemission orbital tomography and density functional calculations to reveal the influence of surface passivation on the molecular geometry and electronic states. We found that the charge transfer into the 7 A molecules on Cu(110) is completely suppressed for the oxygen-modified Cu surface. The molecules are aligned along the Cu-O rows and uncharged. They are tilted due to the geometry enforced by the substrate and the ability to maximize intermolecular π-π overlap, which leads to strong π-band dispersion. The HOMO-LUMO gap of these decoupled molecules is significantly larger than that reported on weakly interacting metal surfaces. Finally, the Cu-O stripe phase was used as a template for nanostructured molecular growth and to assess possible confinement effects.

Reactions of 1,2-Azaborinine, a BN-Benzyne, with Organic π Systems.

Ortho-benzyne and 1,2-azaborinine are related by the formal exchange of the CC triple bond by the isoelectronic BN unit. The (2 + 2) and (2 + 4) cycloaddition reactions of 1,2-azaborinine with the different organic π systems (ethene, ethyne, 1,3-butadiene, 1,3-cyclopentadiene, furan, benzene) were examined computationally using density functional, second-order perturbation, and coupled-cluster methods. All reactions of 1,2-azaborinine with the studied substrates are highly exothermic and involve the formation of Lewis acid-base complexes of 1,2-azaborinine and respective π systems. The interaction between the π bond of the substrates and the empty p orbital of the boron atom in these complexes is remarkably strong, resulting in two-step mechanisms for the (2 + 2) and (2 + 4) cycloaddition reactions. Cycloaddition reactions have lower barriers than CH insertion reactions, and (2 + 4) reactions are favored over (2 + 2) cycloadditions.

Chemical Doping by Fluorination and Its Impact on All Energy Levels of π-Conjugated Systems.

Halogenation of organic molecules causes chemical shifts of C1s core-level binding energies that are commonly used as fingerprints to identify chemical species. Here, we use synchrotron-based X-ray photoelectron spectroscopy and density functional theory calculations to unravel such chemical shifts by examining different partially fluorinated pentacene derivatives. Core-level shifts occur even for carbon atoms distant from the fluorination positions, yielding a continuous shift of about 1.8 eV with increasing degree of fluorination for pentacenes. Since also their LUMO energies shift markedly with the degree of fluorination of the acenes, core-level shifts result in a nearly constant excitation energy of the leading π* resonance as obtained in complementary recorded K-edge X-ray absorption spectra, hence demonstrating that local fluorination affects the entire π-system, including valence and core levels. Our results thus challenge the common picture of characteristic chemical core-level energies as fingerprint signatures of fluorinated π-conjugated molecules.

Boradigermaallyl: (4+3) Cycloaddition-Initiated Boron Insertion into Benzene.

The 2π electron 1,3-dipole boradigermaallyl, valence-isoelectronic to an allyl cation, is synthesized from a bis(germylene). It reacts with benzene at room temperature by insertion of a boron atom into the benzene ring. Computational investigation of the mechanism shows the boradigermaallyl reacting with a benzene molecule in a concerted (4+3) or [π4s+π2s] cycloaddition reaction. Thus, the boradigermaallyl acts as a highly reactive dienophile in this cycloaddition reaction with nonactivated benzene as diene unit. This type of reactivity provides a novel platform for ligand assisted borylene insertion chemistry.

Limited Stability of 6,13-Bis(tri(isopropyl)silylethynyl)pentacene upon One-Electron Oxidation: Electrochemically Induced (4 + 2) Cycloaddition between an Alkynyl-Substituted Acene and Its Radical Cation.

6,13-Bis(tri(isopropyl)silylethynyl)pentacene, a particularly stable acene derivative important for (opto)electronic materials, turns reactive upon electrochemical one-electron oxidation. One of the typically stabilizing tri(isopropyl)silylethynyl substituents becomes involved in a (4 + 2) cycloaddition after redox umpolung. The electrosynthetic dimerization of the title compound provides easy access under mild conditions to a complex scaffold, which includes an intact pentacene, an anthracene, and a phenylene unit, all electronically separated. The product's electrochemical redox properties are explained by superimposed cyclic voltammetric features of the pentacene and the anthracene moieties. The reaction path is analyzed on the basis of electroanalytical and ESR data, and an oxidation-cycloaddition-reduction sequence is elaborated. The contribution of homogeneous electron transfers (electron transfer chain reaction) is negligible, in accordance with the relative formal redox potentials of the starting compound and the product. Quantum chemical calculations indicate that the central cycloaddition should be described as a two-step process with a distonic radical cation intermediate. We suggest an extended notation to define the contribution of the components with respect to electron count in the two-step cycloaddition, [3 + 1, 1 + 1].

Computational Exploration of the Intersystem Crossing from the X̃3A2 to the ã1A1 State in Boryl Nitrenes upon Photoexcitation.

The boryl nitrene CatBN (Cat = catecholato) turns highly reactive toward small inert molecules upon irradiation of its triplet ground state X̃3A2 with light of wavelength λ > 550 nm. A computational study of a model boryl nitrene using complete active space self-consistent field (CASSCF) theory provides evidence for the population of the highly reactive electronic state ã1A1 upon irradiation. Potential energy scans connecting different critical points (minima, minimum energy crossing points, and conical intersections) reveal two possible pathways that could relax photoexcited boryl nitrene from the Franck-Condon region of Ã3B1 to the ã1A1 state minimum. Considering the energy barriers to relaxation from one electronic state to another and the magnitude of spin-orbit couplings, the energetically most favorable pathway involves photoexcitation to Ã3B2, followed by intersystem crossing to the open-shell singlet state (b̃1A2) and internal conversion to ã1A1. The relevant minimum energy crossing point is about 7-8 kcal mol-1 higher in energy than the Franck-Condon region.

Solvation of Large Polycyclic Aromatic Hydrocarbons in Helium: Cationic and Anionic Hexabenzocoronene.

The adsorption of helium on charged hexabenzocoronene (Hbc, C42H18), a planar polycyclic aromatic hydrocarbon (PAH) molecule of D6h symmetry, was investigated by a combination of high-resolution mass spectrometry and classical and quantum computational methods. The ion abundance of HenHbc+ complexes versus size n features prominent local anomalies at n = 14, 38, 68, 82, and a weak one at 26, indicating that for these "magic" sizes, the helium evaporation energies are relatively large. Surprisingly, the mass spectra of anionic HenHbc- complexes feature a different set of anomalies, namely at n = 14, 26, 60, and 62, suggesting that the preferred arrangement of the adsorbate atoms depends on the charge of the substrate. The results of our quantum calculations show that the adsorbate layer grows by successive filling of concentric rings that surround the central benzene ring, which is occupied by one helium atom each on either side of the substrate. The helium atoms are fairly localized in filled rings and they approximately preserve the D6h symmetry of the substrate, but helium atoms in partially filled rings are rather delocalized. The first three rings contain six atoms each; they account for magic numbers at n = 14, 26, and 38. The size of the first ring shrinks as atoms are filled into the second ring, and the position of atoms in the second ring changes from hollow sites to bridge sites as atoms are filled into the third ring. Beyond n = 38, however, the arrangement of helium atoms in the first three rings remains essentially frozen. Presumably, another ring is filled at n = 68 for cations and n = 62 for anions. The calculated structures and energies do not account for the difference between charge states, although they agree with the measurements for the cations and show that the first solvation shell of Hbc± is complete at n = 68. Beyond that size, the adsorbate layer becomes three-dimensional, and the circular arrangement of helium changes to hexagonal.

Hexacene on Cu(110) and Ag(110): Influence of the Substrate on Molecular Orientation and Interfacial Charge Transfer.

Hexacene, composed of six linearly fused benzene rings, is an organic semiconductor material with superior electronic properties. The fundamental understanding of the electronic and chemical properties is prerequisite to any possible application in devices. We investigate the orientation and interface properties of highly ordered hexacene monolayers on Ag(110) and Cu(110) with X-ray photoemission spectroscopy (XPS), photoemission orbital tomography (POT), X-ray absorption spectroscopy (XAS), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT). We find pronounced differences in the structural arrangement of the molecules and the electronic properties at the metal/organic interfaces for the two substrates. While on Cu(110) the molecules adsorb with their long molecular axis parallel to the high symmetry substrate direction, on Ag(110), hexacene adsorbs in an azimuthally slightly rotated geometry with respect to the metal rows of the substrate. In both cases, molecular planes are oriented parallel to the substrate. A pronounced charge transfer from both substrates to different molecular states affects the effective charge of different C atoms of the molecule. Through analysis of experimental and theoretical data, we found out that on Ag(110) the LUMO of the molecule is occupied through charge transfer from the metal, whereas on Cu(110) even the LUMO+1 receives a charge. Interface dipoles are determined to a large extent by the push-back effect, which are also found to differ significantly between 6A/Ag(110) and 6A/Cu(110).

Kinetic stabilization allows structural analysis of a benzoborirene.

Formal reduction of (2-bromophenyl)chloro(2,2'',4,4'',6,6''-hexaisopropyl-[1,1':3',1''-terphenyl]-2'-yl)borane with tert-butyl lithium at low temperatures yields a highly strained benzoborirene that is kinetically stabilized by the bulky terphenyl substituent. The target compound withstands heating to 80 °C, and represents the first benzoborirene fully characterized by single-crystal X-ray crystallography. The bond length pattern of the six-membered ring of the parent benzoborirene follows an anti-Mills-Nixon distortion.

Solution Phase Reactivity of Dibenzo[c,e][1,2]azaborinine: Activation and Insertion into Si-E Single Bonds (E=H, OSi(CH3 )3 , F, Cl) by a BN-Aryne.

The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si-E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si-E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si-F bond.

Bright Luminescence by Combining Chiral [2.2]Paracyclophane with a Boron-Nitrogen-Doped Polyaromatic Hydrocarbon Building Block.

Novel BN-doped compounds based on chiral, tetrasubstituted [2.2]paracyclophane and NBN-benzo[f,g]tetracene were synthesized by Sonogashira-Hagihara coupling. Conjugated ethynyl linkers allow electronic communication between the π-electron systems through-bond, whereas through-space interactions are provided by strong π-π overlap between the pairs of NBN-building blocks. Excellent optical and chiroptical properties in racemic and enantiopure conditions were measured, with molar absorption coefficients up to ϵ=2.04×105  M-1 cm-1 , fluorescence quantum yields up to ΦPL =0.70, and intense, mirror-image electronic circular dichroism and circularly polarized luminescence signals of the magnitude of 10-3 for the absorption and luminescence dissymmetry factors. Computed glum,calcd. values match the experimental ones. Electroanalytical data show both oxidation and reduction of the ethynyl-linked tetra-NBN-substituted paracyclophane, with an overlap of two redox processes for oxidation leading to a diradical dication.

Permanent Dipole Moments Enhance Electronic Coupling and Singlet Fission in Pentacene.

Singlet fission (SF), the photophysical process in which one singlet exciton is transformed into two triplets, depends inter alia on the coupling of electronic states. Here, we use fluorination and the resulting changes in partial charge distribution across the chromophore backbone as a particularly powerful tool to control this parameter in pentacene. We find that the introduction of a permanent dipole moment leads to an enhanced coupling of Frenkel exciton and charge transfer states and to an increased SF rate which we probed using ultrafast transient absorption spectroscopy. These findings are contrasted with H-aggregate formation and a significantly reduced triplet-pair state lifetime in a fluorinated pentacene for which the different partial charge distribution leads to a negligible dipole moment.

The Reaction of CO2 with a Borylnitrene: Formation of an 3-Oxaziridinone.

The reaction of a borylnitrene with carbon dioxide is studied under cryogenic matrix isolation conditions. Photogenerated CatBN (Cat=catecholato) reacts with CO2 under formation of the cycloaddition product CatBNCO2 , a 3-oxaziridinone derivative, after photoexcitation (>550 nm). The product shows Fermi resonances between the CO stretching and ring deformation modes that cause unusual 13 C and 18 O isotopic shifts. A computational analysis of the 3-oxaziridinone shows this cyclic carbamate to be less strained than an α-lactone or an α-lactame.