Bis-[cyclic(alkyl)(amino)carbene]-derived diradicals.

Crystalline polymeric structures of trans-1,4-cyclohexylene bridged N-tethered bis-CAACs in the form of their LiOTf adducts were synthesized and isolated. These were further used as building blocks for the synthesis of crystalline (amino)(carboxy)-based diradicals. The triplet diradical character of these compounds was unambiguously confirmed by the presence of a half-field signal in their EPR spectra. Theoretical calculations show that the singlet state is marginally more stable than the triplet state.

Push-pull [7]helicene diimide: excited-state charge transfer and solvatochromic circularly polarised luminescence.

In this communication we describe a helically chiral push-pull molecule named 9,10-dimethoxy-[7]helicene diimide, displaying fluorescence (FL) and circularly polarised luminescence (CPL) over nearly the entire visible spectrum dependent on solvent polarity. The synthesised molecule exhibits an unusual solvent polarity dependence of FL quantum yield and nonradiative rate constant, as well as remarkable gabs and glum values along with high configurational stability.

Introducing an orthogonally polarized electron-rich alkene: synthesis of a zwitterionic boron-containing π-conjugated system.

The synthesis of an alkene is reported which is concurrently twisted (twist angle = 86.6(8)°), push-pull (dipole moment = 7.48 D), and electron-rich (E1/2 = -1.45 V and -0.52 V vs. Fc/Fc+) in nature, comprising a unique trinity combination for the alkene class of compounds. Subsequently, this newly synthesized alkene-motif was used as a donor for the synthesis of a zwitterionic boron-containing π-conjugated compound (dipole moment = 12.17 D) through an intramolecular charge transfer process exploiting the π-conjugated donor-acceptor system.

Bis-Olefin Based Crystalline Schlenk Hydrocarbon Diradicals with a Triplet Ground State.

A modular approach for the synthesis of isolable crystalline Schlenk hydrocarbon diradicals from m-phenylene bridged electron-rich bis-triazaalkenes as synthons is reported. EPR spectroscopy confirms their diradical nature and triplet electronic structure by revealing a half-field signal. A computational analysis confirms the triplet state to be the ground state. As a proof-of-principle for the modular methodology, the 4,6-dimethyl-m-phenylene was further utilized as a coupling unit between two alkene motifs. The steric conjunction of the 4,6-dimethyl groups substantially twists the substituents at the nonbonding electron bearing centers relative to the central coupling m-phenylene motif. As a result, the spin delocalization is decreased and the exchange coupling between the two unpaired spins, hence, significantly reduced. Notably, 108 years after Schlenk's m-phenylene-bis(diphenylmethyl) synthesis as a diradical, for the first time we were able to isolate its derivative with the same spacer, i.e. m-phenylene, between two radical centers in a crystalline form.

Dimethylnonacethrene - en route to a magnetic switch.

Dimethylnonacethrene is the first derivative of the cethrene family that is energetically more stable than the product of its electrocyclic ring closure. Compared to the shorter homologue dimethylcethrene, the new system is EPR-active, because of a significantly lowered singlet-triplet gap, and displays remarkable stability. Our results suggest that adjustment of the steric bulk in the fjord region can enable realisation of diradicaloid-based magnetic photoswitches.

Efficient Narrowband Circularly Polarized Light Emitters Based on 1,4-B,N-embedded Rigid Donor-Acceptor Helicenes.

Narrow-band emission is essential for applicable circularly polarized luminescence (CPL) active materials in ultrahigh-definition CP-OLEDs. One of the most promising classes of CPL active molecules, helicenes, however, typically exhibit broad emission with a large Stokes shift. We present, herein, a design strategy capitalizing on intramolecular donor-acceptor interactions between nitrogen and boron atoms to address this issue. 1,4-B,N-embedded configurationally stable single- and double helicenes were synthesized straightforwardly. Both helicenes show unprecedentedly narrow fluorescence and CPL bands (full width at half maximum between 17-28 nm, 0.07-0.13 eV) along with high fluorescence quantum yields (72-85 %). Quantum chemical calculations revealed that the relative localization of the natural transition orbitals, mainly on the rigid core of the molecule, and small values of root-mean-square displacements between S0 and S1 state geometries, contribute to the narrower emission.

A bis-NHC-CAAC dimer derived dicationic diradical.

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a trans-1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy. The variable temperature EPR study suggests the singlet state to be marginally more stable than the triplet state (2J = -5.5 cm-1 (ΔE ST = 0.065 kJ mol-1)). The presence of the trans-1,4-cyclohexylene bridge is instrumental for the successful isolation of this dicationic diradical. Notably, in the case of ethylene or propylene bridged bis-NHC-CAAC dimers, the corresponding dicationic diradicals are transient and rearrange to hydrogen abstracted products.

Nonacethrene Unchained: A Cascade to Chiral Contorted Conjugated Hydrocarbon with Two sp3-Defects.

We demonstrate that structurally complex carbon nanostructures can be achieved via a synthetic approach that capitalizes on a π-radical reaction cascade. The cascade is triggered by oxidation of a dihydro precursor of helical diradicaloid nonacethrene to give a chiral contorted polycyclic aromatic hydrocarbon named hypercethrene. In this ten-electron oxidation process, four σ-bonds, one π-bond, and three six-membered rings are formed in a sequence of up to nine steps to yield a 72-carbon-atom warped framework, comprising two configurationally locked [7]helicene units, a fluorescent peropyrene unit, and two precisely installed sp3-defects. The key intermediate in this cascade is a closed nonacethrene derivative with one quaternary sp3-center, presumably formed via an electrocyclic ring closure of nonacethrene, which, when activated by oxidation, undergoes a reaction cascade analogous to the oxidative dimerization of phenalenyl to peropyrene. By controlling the amount of oxidant used, two intermediates and one side product could be isolated and fully characterized, including single-crystal X-ray diffraction analysis, and two intermediates were detected by electron paramagnetic resonance spectroscopy. In concert with density functional theory calculations, these intermediates support the proposed reaction mechanism. Compared to peropyrene, the absorption and emission of hypercethrene are slightly red-shifted on account of extended π-conjugation and the fluorescence quantum yield of 0.45 is decreased by a factor of ∼2. Enantiomerically enriched hypercethrene displays circularly polarized luminescence with a brightness value of 8.3 M-1 cm-1. Our results show that reactions of graphene-based π-radicals-typically considered an "undefined decomposition" of non-zero-spin materials-can be well-defined and selective, and have potential to be transformed into a step-economic synthetic method toward complex carbon nanostructures.

Pyrene-Fused [7]Helicenes Connected Via Hexagonal and Heptagonal Rings: Stereospecific Synthesis and Chiroptical Properties.

In this manuscript, we portrayed a stereospecific synthesis of C2- and C1-symmetric pyrene-fused [7]helicene compounds 1 and 2, respectively. Compounds 1 and 2 were synthesized via a one-pot Suzuki coupling-C-H activation and two-step Suzuki coupling-Scholl reaction, respectively, with complete retention of configuration. The synthesized molecules differ in the fusing mode of [7]helicene units with pyrene via six- and seven-membered rings for 1 and 2, respectively. There was a significant difference in the functional properties and enantiomerization barrier of both compounds because of their distinct molecular symmetry as well as fusing mode to pyrene moiety. The heptagon-containing molecule 2 showed remarkable photophysical and chiroptical properties with commendable configurational stability compared to 1 and pristine [7]helicene as well as its [5]helicene congener.

De Novo Synthesis of Free-Standing Flexible 2D Intercalated Nanofilm Uniform over Tens of cm2.

Of a variety of intercalated materials, 2D intercalated systems have attracted much attention both as materials per se, and as a platform to study atoms and molecules confined among nanometric layers. High-precision fabrication of such structures has, however, been a difficult task using the conventional top-down and bottom-up approaches. The de novo synthesis of a 3-nm-thick nanofilm intercalating a hydrogen-bonded network between two layers of fullerene molecules is reported here. The two-layered film can be further laminated into a multiply film either in situ or by sequential lamination. The 3 nm film forms uniformly over an area of several tens of cm2 at an air/water interface and can be transferred to either flat or perforated substrates. A free-standing film in air prepared by transfer to a gold comb electrode shows proton conductivity up to 1.4 × 10-4 S cm-1 . Electron-dose-dependent reversible bending of a free-standing 6-nm-thick nanofilm hung in a vacuum is observed under electron beam irradiation.

Diamidocarbene-Based Thiele and Tschitschibabin Hydrocarbons: Carbonyl Functionalized Kekulé Diradicaloids.

Herein, we report diamidocarbene (DAC)-based Thiele and Tschitschibabin hydrocarbons, diradicaloids that contain four carbonyl/amido functional groups. The impact of two different π-conjugated spacers, p-phenylene vs p,p'-biphenylene, has been realized. The quantum chemical calculations suggest diamidocarbene (DAC)-based Thiele hydrocarbon (p-phenylene bridged) closed-shell singlet is the ground state, whereas for the diamidocarbene (DAC)-based Tschitschibabin hydrocarbon (p,p'-biphenylene bridged), open-shell singlet is the ground state. The influence of two different π-conjugated spacers also has been reflected in their UV-vis spectra. To gain more information on the diamidocarbene (DAC)-based Thiele and Tschitschibabin hydrocarbons, we have also carried out cyclic voltammetry investigations along with UV-vis-NIR-spectroelectrochemical studies of their corresponding 2-e oxidized product.

Zinc-[7]helicenocyanine and Its Discrete π-Stacked Homochiral Dimer.

In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×106  M-1 and 3.42×107  M-1 in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn-7HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.

Anionic Boron- and Carbon-Based Hetero-Diradicaloids Spanned by a p-Phenylene Bridge.

Herein we report the synthesis and characterization of anionic boron- and carbon-based Kekulé diradicaloids spanned by a p-phenylene bridge. In contrast to Thiele's hydrocarbon, a closed-shell singlet system, they show an appreciable population of the triplet state at room temperature, as evidenced by both NMR and EPR spectroscopy. Moreover, en route to these anionic boron- and carbon-based hetero-diradicaloids, the formation of an isolable diamino(4-diarylboryl-phenyl)methyl radical was observed.

Nano- and Microspheres Containing Inorganic and Biological Nanoparticles: Self-Assembly and Electron Tomographic Analysis.

Organofullerene amphiphiles show diverse behaviors in water, forming vesicles, micelles, Langmuir-Blodgett films, and anisotropic nanostructures. We found that gradual in situ protonation of an organic solution of (4-heptylphenyl)5C60-K+ by water or buffer generates the corresponding protonated molecule, (4-heptylphenyl)5C60H, which self-assembles to form nano- and microspheres of organofullerene (fullerspheres) with uniform diameters ranging from 30 nm to 2.5 µm that are controlled by the preparation or pH of the buffer. By using an aqueous solution of an organic dye, inorganic nanoparticle, protein, and virus, we encapsulated these entities in the fullersphere. This approach via self-assembly is distinct from other preparations of organic core-shell particles that generally require polymerization for the construction of a robust shell. The sphere is entirely amorphous, thermally stable up to 300 °C under vacuum, and resistant to electron irradiation, and we found the unconventional utility of the sphere for electron tomographic imaging of nanoparticles and biomaterials.

C2- and C1-Symmetric Configurationally Stable Pyrene-Fused [5]Helicenes Connected via Hexagonal and Heptagonal Rings.

In this paper, we describe the stereospecific synthesis and functional properties of C2- and C1-symmetric pyrene-fused [5]helicene molecules 1 and 2 connected via hexagonal and heptagonal rings, respectively. Both molecules showed high configurational stability and distinct functional properties, which were attributed to the fusing mode of [5]helicene with the pyrene and molecular symmetry. The estimated Gibbs activation energy for enantiomerization of 2 is one of the highest reported values for any π-conjugated molecules incorporating [5]helicene moiety.

Carbo[n]helicenes Restricted to Enantiomerize: An Insight into the Design Process of Configurationally Stable Functional Chiral PAHs.

The most important stereodynamic feature of carbo[n]helicenes is the interconversion of their enantiomers. The Gibbs activation energy (ΔG≠ (T)) of this process, which determines the rate of enantiomerization, dictates the configurational stability of [n]helicenes. High values of ΔG≠ (T) are required for applications of functional chiral molecules incorporating [n]helicenes or helicene substructures. This minireview provides an overview of the mechanism, recent developments, and factors affecting the enantiomerization of [n]helicenes, which will accelerate the design process of configurationally stable functional chiral molecules based on helicene substructures. Additionally, this minireview addresses the misconception and irregularities in the recent literature on how the terms "racemization" and "enantiomerization" are used as well as how the activation parameters are calculated for [n]helicenes and related compounds.

[n]Helicene Diimides (n = 5, 6, and 7): Through-Bond versus Through-Space Conjugation.

The interactions between auxochromic groups in π-conjugated functional molecules dictate their electronic properties. From the standpoint of potential applications, understanding and control of such interactions is a vital requirement for the material design. In this communication, we describe the design, synthesis, and functional properties of a novel class of helically chiral diimide molecules, namely, [n]HDI-OMe (n = 5, 6, and 7), in which two imide units are connected via an [n]helicene skeleton. The experimental results supported by quantum chemical calculations reveal that the helical backbone in these molecules offers not only through-bond but also through-space conjugation between imide groups, which leads to distinct optical and electrochemical properties when compared to the related [n]helicenes and rylene diimides.

Benzo[cd]triangulene: A Spin 1/2 Graphene Fragment.

How does edge modification affect spin distribution in open-shell graphene fragments? We investigated this effect by analyzing spin-delocalization in benzo[cd]-triangulene, a spin 1/2 graphene fragment composed of seven benzenoid rings fused in a hybrid zigzag/armchair fashion. Six rings of this system form the core of Clar's hydrocarbon triangulene, to which an additional ring is annulated in the zigzag region. The singly occupied molecular orbital (SOMO) of this hydrocarbon radical resembles both SOMOs of triangulene, but the spin density is distributed over the core in a nonuniform fashion. The uneven spin distribution is reflected in the reactivity-reaction with oxygen occurs selectively at a position with the highest spin density-and correlates nicely with relative stabilities of the corresponding Clar resonance structures. The spin distribution is different from that of a topologically similar compound composed of the same number of sp2 carbon atoms but featuring six rings only, illustrating the impact of subtle structural changes on spin-density distribution. This compound was characterized by means of UV-vis and electron paramagnetic resonance spectroscopy, cyclic voltammetry, mass spectrometry, and X-ray crystallography. The experimental results are supported by density functional theory calculations.