Tetrahedraphene: A Csp3 -centered 3D Molecular Nanographene Showing Aggregation-Induced Emission.

The bottom-up synthesis of 3D tetrakis(hexa-peri-hexabenzocoronenyl)methane, "tetrahedraphene", is reported. This molecular nanographene constituted by four hexa-peri-hexabenzocoronene (HBC) units attached to a central sp3 carbon atom, shows a highly symmetric arrangement of the HBC units disposed in the apex of a tetrahedron. The X-ray crystal structure reveals a tetrahedral symmetry of the molecule and the packing in the crystal is achieved mostly by CH⋅⋅⋅π interactions since the interstitial solvent molecules prevent the π⋅⋅⋅π interactions. In solution, tetrahedraphene shows the same electrochemical and photophysical properties as the hexa-t Bu-substituted HBC (t Bu-HBC) molecule. However, upon water addition, it undergoes a fluorescence change in solution and in the precipitated solid, showing an aggregation induced emission (AIE) process, probably derived from the restriction in the rotation and/or vibration of the HBCs. Time-Dependent Density Functional Theory (TDDFT) calculations reveal that upon aggregation, the high energy region of the emission band decreases in intensity, whereas the intensity of the red edge emission signal increases and presents a smoother decay, compared to the non-aggregated molecule. All in all, the excellent correlation between our simulations and the experimental findings allows explaining the colour change observed in the different solutions upon increasing the water fraction.

Helical Bilayer Nanographenes: Impact of the Helicene Length on the Structural, Electrochemical, Photophysical, and Chiroptical Properties.

Helical bilayer nanographenes (HBNGs) are chiral π-extended aromatic compounds consisting of two π-π stacked hexabenzocoronenes (HBCs) joined by a helicene, thus resembling van der Waals layered 2D materials. Herein, we compare [9]HBNG, [10]HBNG, and [11]HBNG helical bilayers endowed with [9], [10], and [11]helicenes embedded in their structure, respectively. Interestingly, the helicene length defines the overlapping degree between the two HBCs (number of benzene rings involved in π-π interactions between the two layers), being 26, 14, and 10 benzene rings, respectively, according to the X-ray analysis. Unexpectedly, the electrochemical study shows that the lesser π-extended system [9]HBNG shows the strongest electron donor character, in part by interlayer exchange resonance, and more red-shifted values of emission. Furthermore, [9]HBNG also shows exceptional chiroptical properties with the biggest values of gabs and glum (3.6 × 10-2) when compared to [10]HBNG and [11]HBNG owing to the fine alignment in the configuration of [9]HBNG between its electric and magnetic dipole transition moments. Furthermore, spectroelectrochemical studies as well as the fluorescence spectroscopy support the aforementioned experimental findings, thus confirming the strong impact of the helicene length on the properties of this new family of bilayer nanographenes.

Curved Nanographenes: Multiple Emission, Thermally Activated Delayed Fluorescence, and Non-Radiative Decay.

The intriguing and rich photophysical properties of three curved nanographenes (CNG 6, 7, and 8) are investigated by time-resolved and temperature-dependent photoluminescence (PL) spectroscopy. CNG 7 and 8 exhibit dual fluorescence, as well as dual phosphorescence at low temperature in the main PL bands. In addition, hot bands are detected in fluorescence as well as phosphorescence, and, in the narrow temperature range of 100-140 K, thermally activated delayed fluorescence (TADF) with lifetimes on the millisecond time-scale is observed. These findings are rationalized by quantum-chemical simulations, which predict a single minimum of the S1 potential of CNG 6, but two S1 minima for CNG 7 and CNG 8, with considerable geometric reorganization between them, in agreement with the experimental findings. Additionally, a higher-lying S2 minimum close to S1 is optimized for the three CNG, from where emission is also possible due to thermal activation and, hence, non-Kasha behavior. The presence of higher-lying dark triplet states close to the S1 minima provides mechanistic evidence for the TADF phenomena observed. Non-radiative decay of the T1 state appears to be thermally activated with activation energies of roughly 100 meV and leads to disappearance of phosphorescence and TADF at T > 140 K.

Electronic Control of the Scholl Reaction: Selective Synthesis of Spiro vs Helical Nanographenes.

Scholl oxidation has become an essential reaction in the bottom-up synthesis of molecular nanographenes. Herein, we describe a Scholl reaction controlled by the electronic effects on the starting substrate (1 a, b). Anthracene-based polyphenylenes lead to spironanographenes under Scholl conditions. In contrast, an electron-deficient anthracene substrate affords a helically arranged molecular nanographene formed by two orthogonal dibenzo[fg,ij]phenanthro-[9,10,1,2,3-pqrst]pentaphene (DBPP) moieties linked through an octafluoroanthracene core. Density Functional Theory (DFT) calculations predict that electronic effects control either the first formation of spirocycles and subsequent Scholl reaction to form spironanographene 2, or the expected dehydrogenation reaction leading solely to the helical nanographene 3. The crystal structures of four of the new spiro compounds (syn 2, syn 9, anti 9 and syn 10) were solved by single crystal X-ray diffraction. The photophysical properties of the new molecular nanographene 3 reveal a remarkable dual fluorescent emission.

Stepwise reduction of a corannulene-based helical molecular nanographene with Na metal.

The chemical reduction of a corannulene-based molecular nanographene, C76H64 (1), with Na metal in the presence of 18-crown-6 afforded the doubly-reduced state of 1. This reduction provokes a distortion of the helicene core and has a significant impact on the aromaticity of the system.

Synthetic chiral molecular nanographenes: the key figure of the racemization barrier.

Chirality is one of the most intriguing concepts of chemistry, involving living systems and, more recently, materials science. In particular, the bottom-up synthesis of molecular nanographenes endowed with one or several chiral elements is a current challenge for the chemical community. The wilful introduction of defects in the sp2 honeycomb lattice of molecular nanographenes allows the preparation of chiral molecules with tuned band-gaps and chiroptical properties. There are two requirements that a system must fulfill to be chiral: (i) lack of inversion elements (planes or inversion centres) and (ii) to be configurationally stable. The first condition is inherently established by the symmetry group of the structure, however, the limit between conformational and configurational isomers is not totally clear. In this feature article, the chirality and dynamics of synthetic molecular nanographenes, with special emphasis on their racemization barriers and, therefore, the stability of their chiroptical properties are discussed. The general features of nanographenes and their bottom-up synthesis, including the main defects inducing chirality in molecular nanographenes are firstly discussed. In this regard, the most common topological defects of molecular NGs as well as the main techniques used for determining their energy barriers are presented. Then, the manuscript is structured according to the dynamics of molecular nanographenes, classifying them in four main groups, depending on their respective isomerization barriers, as flexible, detectable, isolable and rigid nanographenes. In these sections, the different strategies used to increase the isomerization barrier of chiral molecular nanographenes that lead to configurationally stable nanographenes with defined chiroptical properties are discussed.

Initiating Electron Transfer in Doubly Curved Nanographene Upon Supramolecular Complexation of C60.

The formation of supramolecular complexes between C60 and a molecular nanographene endowed with both positive and negative curvatures is described. The presence of a corannulene moiety and the saddle shape of the molecular nanographene allows the formation of complexes with 1:1, 1:2, and 2:1 stoichiometries. The association constants for the three possible supramolecular complexes were determined by 1 H NMR titration. Furthermore, the stability of the three complexes was calculated by theoretical methods that also predict the photoinduced electron transfer from the curved nanographene to the electron acceptor C60 . Time-resolved transient absorption measurements on the ns-time scale showed that the addition of C60 to NG-1 solutions and photo-exciting them at 460 nm leads to the solvent-dependent formation of new species, in particular the formation of the one-electron reduced form of C60 in benzonitrile was observed.

Site-Specific Reduction-Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb+ Complexation.

The chemical reduction of π-conjugated bilayer nanographene 1 (C138 H120 ) with K and Rb in the presence of 18-crown-6 affords [K+ (18-crown-6)(THF)2 ][{K+ (18-crown-6)}2 (THF)0.5 ][C138 H122 3- ] (2) and [Rb+ (18-crown-6)2 ][{Rb+ (18-crown-6)}2 (C138 H122 3- )] (3). Whereas K+ cations are fully solvent-separated from the trianionic core thus affording a "naked" 1.3 - anion, Rb+ cations are coordinated to the negatively charged layers of 1.3 - . According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site-specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction-induced site-specific hydrogenation provokes dramatic changes in the (electronic) structure of 1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers.

Helically Arranged Chiral Molecular Nanographenes.

A benchtop solution-phase synthesis of molecular nanographenes composed of two orthogonal dibenzo[fg,ij]phenanthro[9,10,1,2,3-pqrst]pentaphene (DBPP) moieties covalently connected through a tetrafluorobenzene ring is described. The helical arrangement of these three covalently linked molecular fragments leads to the existence of a chiral axis which gives rise to a racemic mixture, even with the molecular moieties being symmetrically substituted. X-ray diffraction studies show that both enantiomers cocrystallize in a single crystal, and the racemic mixture can be resolved by chiral HPLC. Asymmetric substitution in DBPP moieties affords a pair of diastereoisomers whose rotational isomerization has been studied by 1H NMR. Additionally, the electrochemical and photophysical properties derived from these new molecular nanographenes reveal an electroactive character and a significant fluorescent behavior.

Chiral Molecular Carbon Nanostructures.

Chirality is a fascinating property present in naturally occurring and artificial molecules and materials, observable as chiroptical behavior. The emerging area of carbon nanostructures has undergone tremendous development, with a wide variety of carbon nanoforms reported over the last two decades. However, despite interest in merging chirality and nanocarbons, this has been successfully achieved only in empty fullerenes, whereas in other kinds of fullerenes or carbon nanostructures such as carbon nanotubes, graphene, and graphene quantum dots (GQDs), to name the most popular systems, it is almost unknown. Therefore, controlling chirality in carbon nanostructures currently represents a major challenge for the chemical community. In this Account, we show our progress in the synthesis of chiral molecular carbon nanostructures, namely, metallofullerenes, endohedral fullerenes, GQDs, and curved molecular nanographenes, by using asymmetric catalysis and both top-down and bottom-up chemical approaches. Furthermore, we bring in a new family of lesser-known molecular chiral bilayer nanographenes, where chirality is introduced from the starting helicene moiety and a single enantiomer of the nanographene is synthesized. Some important landmarks in the development of chiral molecular carbon nanostructures shown in this Account are the application of synthesis-tailored, enantiomerically pure metallofullerenes as catalysts for hydrogen transfer reactions and the use of endohedral fullerenes to determine the effect of the incarcerated molecule in the carbon cage on the cis-trans stereoisomerization of optically active pendent moieties. Furthermore, the first top-down synthesis of chiral GQDs by functionalization with chiral alcohols is also presented. An emerging alternative to GQDs, when the desire for purity and atomistic control outweighs the cost of multistep synthesis, is the bottom-up approach, in which molecular nanographenes are formed in precise sizes and shapes and enantiomeric control is feasible. In this regard, a singular and amazing example is given by our synthesis of a single enantiomer of the first chiral bilayer nanographene, which formally represents a new family of molecular nanographenes with chirality controlled and maintained throughout their syntheses. The aforementioned synthetic chiral nanostructures represent groundbreaking nanocarbon systems where chirality is a further dimension of structural control, paving the way to a new scenario for carbon nanoforms in which chirality selection determines the properties of these novel carbon-based materials. Fine-tuning of such properties is envisioned to impact biomedical and materials science applications.

π-Extended Corannulene-Based Nanographenes: Selective Formation of Negative Curvature.

A geometrically selective bottom-up synthesis of curved nanographenes is described. The synthetic methodology used involves the extension of the π-system of positively curved corannulene by a [4+2] cycloaddition reaction followed by cyclodehydrogenation (Scholl oxidation). By selecting the conditions for the Scholl oxidation, the formation of a seven-membered ring that also confers negative curvature to the resulting nanographene can be activated, offering two topologically distinct, curved nanographenes from a common precursor. Additionally, the structure-property relationship in these new nanographenes is explored via theoretical, electrochemical, photophysical, Raman, and X-ray crystallographic studies.

Regioselective synthesis of oxepinones and azepinones by gold-catalyzed cycloisomerization of functionalyzed cyclopropyl alkynes.

A regioselective synthesis of oxepinones and azepinones in good to excellent yields from alkynylcyclopropanecarboxylic acid derivatives is described. This novel cycloisomerization cascade process consists of a nucleophilic addition followed by a cyclopropane ring-opening, where both donor and acceptor groups are required as substituents of the cyclopropane ring.