Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO-HOMO Inversion in Persistent Radical Cations.

Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust chiroptical properties and a significant stabilization of the excited and ionic radical states. However, this approach has been relatively less explored in the design of persistent organic open-shell systems. We report here the (S,S)-, (R,R)-, and meso-isomers of doubly spiro-conjugated carbocycles featuring flat and rigid carbon-bridged para-phenylenevinylene (CPV) of different conjugation lengths connected by two spiro-carbon centers, which we denote D-spiro-CPV for its quasi-dimeric structure. Our synthetic method based on a double lithiation cyclization approach enables facile production of D-spiro-CPV. D-spiro-CPVs exhibit circularly polarized luminescence (CPL) with high fluorescence quantum yields (ΦFL) resulting in a high CPL brightness of 21 M-1 cm-1 and also exhibit high thermal and photostability. The monoradical cation of D-spiro-CPV absorbing near-infrared light is notably persistent, exhibiting a half-life of 570 h under ambient conditions due to doubly spiro-conjugative stabilization. Theoretical and electrochemical studies indicate the radical cation of D-spiro-CPVs presents a non-Aufbau electron filling, exhibiting inversion of the energy level of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbitals with the SOMO level even below the HOMO-1 level (double SHI effect). Our discoveries provide valuable insights into non-Aufbau molecules and the development of configurationally stable, optically active persistent radicals.

Boosting quantum yields and circularly polarized luminescence of penta- and hexahelicenes by doping with two BN-groups.

The incorporation of boron-nitrogen (BN) units into polycyclic aromatic hydrocarbons (PAHs) as an isoelectronic replacement of two carbon atoms can significantly improve their optical properties, while the geometries are mostly retained. We report the first non-π-extended penta- and hexahelicenes comprising two aromatic 1,2-azaborinine rings. Comparing them with their all-carbon analogs regarding structural, spectral and (chir)optical properties allowed us to quantify the impact of the heteroatoms. In particular, BN-hexahelicene BN[6] exhibited a crystal structure congruent with its analog CC[6], but displayed a fivefold higher fluorescence quantum yield (φfl = 0.17) and an outstanding luminescence dissymmetry factor (|glum| = 1.33 × 10-2). Such an unusual magnification of both properties at the same time makes BN-helicenes suitable candidates as circularly polarized luminescence emitters for applications in materials science.

Supramolecular Large Nanosheets Assembled at Air/Water Interfaces and in Solution from Amphiphilic Heptagon-Containing Nanographenes.

We report the synthesis of a new set of amphiphilic saddle-shaped heptagon-containing polycyclic aromatic hydrocarbons (PAHs) functionalized with tetraethylene glycol chains and their self-assembly into large two-dimensional (2D) polymers. An in-depth analysis of the self-assembly mechanism at the air/water interface has been carried out, and the proposed arrangement models are in good agreement with the molecular dynamics simulations. Quite remarkably, the number and disposition of the tetraethylene glycol chains significantly influence the disposition of the PAHs at the interface and conditionate their packing under pressure. For the three compounds studied, we observed three different behaviors in which the aromatic core is parallel, perpendicular, and tilted with respect to the water surface. We also show that these curved PAHs are able to self-assemble in solution into remarkably large sheets of up to 150 µm2. These results show the relationship, within a family of curved nanographenes, between the monomer configuration and their self-assembly capacity in air/water interfaces and organic-water mixtures.

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene.

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C60 and C70 , with remarkably large binding constants (ca. 107  M-1 ), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes.

On-surface synthesis of non-benzenoid conjugated polymers by selective atomic rearrangement of ethynylarenes.

Here, we report a new on-surface synthetic strategy to precisely introduce five-membered units into conjugated polymers from specifically designed precursor molecules that give rise to low-bandgap fulvalene-bridged bisanthene polymers. The selective formation of non-benzenoid units is finely controlled by the annealing parameters, which govern the initiation of atomic rearrangements that efficiently transform previously formed diethynyl bridges into fulvalene moieties. The atomically precise structures and electronic properties have been unmistakably characterized by STM, nc-AFM, and STS and the results are supported by DFT theoretical calculations. Interestingly, the fulvalene-bridged bisanthene polymers exhibit experimental narrow frontier electronic gaps of 1.2 eV on Au(111) with fully conjugated units. This on-surface synthetic strategy can potentially be extended to other conjugated polymers to tune their optoelectronic properties by integrating five-membered rings at precise sites.

Atomically Precise Distorted Nanographenes: The Effect of Different Edge Functionalization on the Photophysical Properties down to the Femtosecond Scale.

Nanographenes (NGs) have been attracting widespread interest since they combine peculiar properties of graphene with molecular features, such as bright visible photoluminescence. However, our understanding of the fundamental properties of NGs is still hampered by the high degree of heterogeneity usually characterizing most of these materials. In this context, NGs obtained by atomically precise synthesis routes represent optimal benchmarks to unambiguously relate their properties to well-defined structures. Here we investigate in deep detail the optical response of three curved hexa-peri-hexabenzocoronene (HBC) derivatives obtained by atomically precise synthesis routes. They are constituted by the same graphenic core, characterized by the presence of a heptagon ring determining a saddle distortion of their sp2 network, and differ from each other for slightly different edge functionalization. The quite similar structure allows for performing a direct comparison of their spectroscopic features, from steady-state down to the femtosecond scale, and precisely disentangling the role played by the different edge chemistry.

Helical Bilayer Nonbenzenoid Nanographene Bearing a [10]Helicene with Two Embedded Heptagons.

The precision synthesis of helical bilayer nanographenes (NGs) with new topology is of substantial interest because of their exotic physicochemical properties. However, helical bilayer NGs bearing non-hexagonal rings remain synthetically challenging. Here we present the efficient synthesis of the first helical bilayer nonbenzenoid nanographene (HBNG1) from a tailor-made azulene-embedded precursor, which contains a novel [10]helicene backbone with two embedded heptagons. Single-crystal X-ray analysis reveals its highly twisted bilayer geometry with a record small interlayer distance of 3.2 Šamong the reported helical bilayer NGs. Notably, the close interlayer distance between the two layers offers intramolecular through-space conjugation as revealed by in situ spectroelectrochemistry studies together with DFT simulations. Furthermore, the chiroptical properties of the P/M enantiomers of HBNG1 are also evaluated by circular dichroism and circularly polarized luminescence.

Ruthenium nanoparticles canopied by heptagon-containing saddle-shaped nanographenes as efficient aromatic hydrogenation catalysts.

The search for new ligands capable of modifying the metal nanoparticle (MNP) catalytic behavior is of increasing interest. Herein we present the first example of RuNPs stabilized with non-planar heptagon-containing saddle-shaped nanographenes (Ru@1 and Ru@2). The resemblance to graphene-supported MNPs makes these non-planar nanographene-stabilized RuNPs very attractive systems to further investigate graphene-metal interactions. A combined theoretical/experimental study allowed us to explore the coordination modes and dynamics of these nanographenes at the Ru surface. The curvature of these saddle-shaped nanographenes makes them efficient MNP stabilizers. The resulting RuNPs were found to be highly active catalysts for the hydrogenation of aromatics, including platform molecules derived from biomass (i.e. HMF) or liquid organic hydrogen carriers (i.e. N-indole). A significant ligand effect was observed since a minor modification on the hept-HBC structure (C[double bond, length as m-dash]CH2 instead of C[double bond, length as m-dash]O) was reflected in a substantial increase in the MNP activity. Finally, the stability of these canopied RuNPs was investigated by multiple addition experiments, proving to be stable catalysts for at least 96 h.

Highly contorted superhelicene hits near-infrared circularly polarized luminescence.

Herein we describe a novel superhelicene structure consisting of three hexa-peri-hexabenzocoronene (HBC) units arranged in a helical geometry and creating two carbo[5]helicenes and a carbo[7]helicene. The central HBC bears a tropone moiety, which induces a saddle-helix hybrid geometry into the 3D structure of the prepared nanographene. The introduction of multiple helicenes and the position of the tropone unit trigger near-infrared circularly polarized luminescence (NIR-CPL, up to 850 nm, |g lum| = 3.0 × 10-3) combined with good photoluminescence quantum yields (ϕ F = 0.43) and upconverted emission based on two-photon absorption (TPA). Compared to previously reported superhelicenes of similar size, higher quantum yields, CPL brightness, and red-shifted absorption and emission spectra are achieved. Besides, chiroptical properties of enantiopure thin films were evaluated. These findings place this novel superhelicene as the first NIR-CPL superhelicene ever reported and make it a promising candidate for use as a chiral luminescent material in optoelectronic devices.

Aggregation-Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl-Based Cyclophanes.

Here, we report an approach to the synthesis of highly charged enantiopure cyclophanes by the insertion of axially chiral enantiomeric binaphthyl fluorophores into the constitutions of pyridinium-based macrocycles. Remarkably, these fluorescent tetracationic cyclophanes exhibit a significant AIE compared to their neutral optically active binaphthyl precursors. A combination of theoretical calculations and time-resolved spectroscopy reveal that the AIE originates from limited torsional vibrations associated with the axes of chirality present in the chiral enantiomeric binaphthyl units and the fine-tuning of their electronic landscape when incorporated within the cyclophane structure. Furthermore, these highly charged enantiopure cyclophanes display CPL responses both in solution and in the aggregated state. This unique duality of AIE and CPL in these tetracationic cyclophanes is destined to be of major importance in future development of photonic devices and bio-applications.

Circularly Polarized Luminescence in a Möbius Helicene Carbon Nanohoop.

We present the first helicene carbon nanoohop that integrates a [6]helicene into [7]cycloparaphenylene. The [6]helicene endows the helicene carbon nanohoop with chiroptical properties and configurational stability typical for higher helicenes, while the radially conjugated seven para-phenylenes largely determine the optoelectronic properties. The structure of the helicene carbon nanoohop was unambiguously characterized by NMR, MS and X-ray analysis that revealed that it possesses a topology of a Möbius strip in the solid state and in solution. The chirality transfers from the [6]helicene to the para-phenylenes and leads to a pronounced circular dichroism and bright circularly polarized luminescence, which is affected by the structural topology of the nanohoop.

On-Surface Thermal Stability of a Graphenic Structure Incorporating a Tropone Moiety.

On-surface synthesis, complementary to wet chemistry, has been demonstrated to be a valid approach for the synthesis of tailored graphenic nanostructures with atomic precision. Among the different existing strategies used to tune the optoelectronic and magnetic properties of these nanostructures, the introduction of non-hexagonal rings inducing out-of-plane distortions is a promising pathway that has been scarcely explored on surfaces. Here, we demonstrate that non-hexagonal rings, in the form of tropone (cycloheptatrienone) moieties, are thermally transformed into phenyl or cyclopentadienone moieties upon an unprecedented surface-mediated retro-Buchner-type reaction involving a decarbonylation or an intramolecular rearrangement of the CO unit, respectively.

Chiral Distorted Hexa-peri-hexabenzocoronenes Bearing a Nonagon-Embedded Carbohelicene.

A new family of chiral saddle-helix hybrid nanographenes is reported. The first hexa-peri-hexabenzocoronene (HBC) analogues bearing a nine-membered carbocycle are presented. Furthermore, for the first time, π-extended carbo[n]helicenes containing a nine-membered ring as part of the helical moiety have been synthesized. The combination of a [5]helicene moiety and a nonagon ring in a single chiral motif induces a tremendous distortion from planarity into the nanographenic structures compared to other saddle-helix hybrids such as heptagon- and octagon-containing π-extended carbo[5]helicenes. In fact, the interplanar angle of the two terminal rings reaches the largest angle (134.8°) of a carbohelicene reported to date, thus being by far the most twisted helicene yet prepared. Photophysical properties evaluation showed improved absorption dissymmetry factors (|gabs |=4.2×10-3 ) in the new family of nonagon-containing π-extended carbo[5]helicenes.

Bright Long-Lived Circularly Polarized Luminescence in Chiral Chromium(III) Complexes.

A series of highly emissive inert and chiral CrIII complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized. The helical [Cr(dqpR)2 ]3+ (dqp=2,6-di(quinolin-8-yl)pyridine; R=OCH3 , Br or C≡CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC. The corresponding enantiomers show large glum ≈0.2 and high quantum yield of up to 17 %, which afford important CPL brightness of up to 170 m-1 cm-1 , a key point for applications as chiral luminescent probes. Moreover, the long-lived CP-NIR emission provided by these chromophores (ms range) in aqueous solution opens the way toward the quantification of chiral targets in biological systems with time-gated detection. Thus, such chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal-based complexes.

Octagon-Embedded Carbohelicene as a Chiral Motif for Circularly Polarized Luminescence Emission of Saddle-Helix Nanographenes.

We report a new family of hexa-peri-hexabenzocoronene (HBC)-based helical nanographenes incorporating π-extended carbo[5]helicenes bearing an octagonal carbocycle. This family represents a new kind of highly distorted saddle-helix hybrid nanographenes. For the first time, the eight-membered ring becomes a constituent of both a carbo[5]helicene and a HBC and thus, the negative curvature is responsible for twisting both units. This novel chiral motif, namely, oct-[5]helicene results in the largest torsion angle recorded so far for a carbo[5]helicene (θ=79.5°), as it has been suggested by DFT-calculations and confirmed by X-ray crystallography. Consequently, the barriers of isomerization become exceptionally high for a [5]helicene unsubstituted in the fjord region since neither racemization nor decomposition were observed at 200 °C for 1 or 3 during 5 h. Therefore, racemic resolutions allowed subsequent chiroptical studies showing the ECD and CPL responses of this novel family of chiral nanographenes.

Single-Molecule Conductance of 1,4-Azaborine Derivatives as Models of BN-doped PAHs.

The single-molecule conductance of a series of BN-acene-like derivatives has been measured by using scanning tunneling break-junction techniques. A strategic design of the target molecules has allowed us to include azaborine units in positions that unambiguously ensure electron transport through both heteroatoms, which is relevant for the development of customized BN-doped nanographenes. We show that the conductance of the anthracene azaborine derivative is comparable to that of the pristine all-carbon anthracene compound. Notably, this heteroatom substitution has also allowed us to perform similar measurements on the corresponding pentacene-like compound, which is found to have a similar conductance, thus evidencing that B-N doping could also be used to stabilize and characterize larger acenes for molecular electronics applications. Our conclusions are supported by state-of-the-art transport calculations.

Dibenzocycloheptatriene as end-group of Thiele and tetrabenzo-Chichibabin hydrocarbons.

Thiele (Th) and tetrabenzo-Chichibabin (TBC) derivatives with terminal dibenzocycloheptatriene (DBHept) units were prepared. A clear correlation between their electronic and molecular structures was stablished. Insights into their closed- or open-shell ground states were gained, where particular contribution of the heptagonal carbocycles as end-groups was proved. Remarkably, a thermally accessible triplet diradical configuration was confirmed for the DBHept-TBC compound.

A Macrocycle Based on a Heptagon-Containing Hexa-peri-hexabenzocoronene.

A cyclophane is reported incorporating two units of a heptagon-containing extended polycyclic aromatic hydrocarbon (PAH) analogue of the hexa-peri-hexabenzocoronene (HBC) moiety (hept-HBC). This cyclophane represents a new class of macrocyclic structures that incorporate for the first time seven-membered rings within extended PAH frameworks. The saddle curvature of the hept-HBC macrocycle units induced by the presence of the nonhexagonal ring along with the flexible alkyl linkers generate a cavity with shape complementarity and appropriate size to enable π interactions with fullerenes. Therefore, the cyclophane forms host-guest complexes with C60 and C70 with estimated binding constants of Ka =420±2 m-1 and Ka =(6.49±0.23)×103 m-1 , respectively. As a result, the macrocycle can selectively bind C70 in the presence of an excess of a mixture of C60 and C70 .

Simple Perylene Diimide Cyclohexane Derivative With Combined CPL and TPA Properties.

In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a glum in the range of 10-3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500-600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650-750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons.

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.