Carlos M. Cruz

University of Granada | UGR

Nanographenes (NGs) are attracting significant interest as atomically‐thin carbon‐based optical nanomaterials exhibiting a wide range of optical properties that are fine‐tuned with ultimate atomic precision though chemical design. However, the use of NGs in photonic applications remains poorly explored. Here a straightforward procedure is demonstra...

A pair of enantiopure [6]‐azairidahelicenes incorporating chirality at the metal center and on the helicenic ligand were synthesized by dynamic kinetic resolution (dkr) of a configurationally labile [4]‐helicenic ligand (4‐(2‐pyridyl)‐benzo[g]phenanthrene, L1H) using bis‐cyclometalated chiral‐at‐metal only iridium(III) precursors as chiral inductor...

A pair of enantiopure [6]‐azairidahelicenes incorporating chirality at the metal center and on the helicenic ligand were synthesized by dynamic kinetic resolution (dkr) of a configurationally labile [4]‐helicenic ligand (4‐(2‐pyridyl)‐benzo[g]phenanthrene, L1H) using bis‐cyclometalated chiral‐at‐metal only iridium(III) precursors as chiral inductor...

The synthesis and the optoelectronic, magnetic and chiroptical properties of a helically chiral diradicaloid have been reported. Dibenzoindeno[2,1-c]fluorene, the simplest configurationally stable chiral derivative of the family of the indenofluorenes, shows a low HOMO-LUMO gap and a moderate singlet-triplet gap. Enantiomers have been isolated and...

Reactions of open‐shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π‐magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via format...

We resolve the origin of the anomalous circularly polarized luminescence (CPL) observed in helicene para-phenylenes (HPPs), a new class of chiral macrocyclic nanocarbons reported recently. We show by synthesis of HPPs that embed [5]helicene unit that the presence of two emission bands in the CPL, each with the opposite handedness, relates to the to...

Reactions of open‐shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π‐magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via format...

The development of chiral compounds with enhanced chiroptical properties is an important challenge to improve device applications. To that end, an optimization of the electric and magnetic dipole transition moments of the molecule is necessary. Nevertheless, the relationship between chemical structure and such quantum mechanical properties is not a...

The development of chiral compounds with enhanced chiroptical properties is an important challenge to improve device applications. To that end, an optimization of the electric and magnetic dipole transition moments of the molecule is necessary. Nevertheless, the relationship between chemical structure and such quantum mechanical properties is not a...

Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via format...

Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via format...

The combination of different distortion motifs in nanographenes and polycyclic conjugated hydrocarbons has been the focus of significant attention during the last decade. The continual discovery of multiple carbon allotropes has fueled the field. A plethora of research groups around the globe are engaged in developing methods for the preparation of...

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, wit...

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 C 60 and C 70 ,...

In this contribution we report on the synthesis and characterization of NIR-I luminescent silica nanoparticles doped with the chiral luminescent CrIIIN6 complex [Cr(dqp)2]³⁺ (dqp = 2,6-di(quinolin-8-yl)pyridine), [email protected], as well as on their post-functionalization with the highly luminescent Eu(tta)3(phen-Si) (tta = 2-Thenoyltrifluoroacet...

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 th...

Singlet fission is envisaged to enhance the efficiency of single-junction solar cells beyond the current theoretical limit. Even though sensitizers that undergo singlet fission efficiently are known, characteristics like low-energy triplet state or insufficient stability restrict their use in silicon-based solar cells. Pyrenacenes have the potentia...

This book chapter puts helical nanographenes under the spotlight. The appealing combination of chirality and extended conjugation of these purely organic molecular designs makes them promising candidates for optoelectronic applications. Herein, the optical properties of nanographenes presenting helical motifs, both achiral/racemic and enantioenrich...

Currently, the food society is in the transition to the age of information dubbed as 'Industry 4.0' (I4.0) towards automation and data-driven decisions. Recent advances in computer technology and instrumentation engineering for industrial food processing have led to the use of multi/megavariate data analysis by using machine learning/data mining me...

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 introduc...

Three achiral polycyclic aromatic fluorophores─namely, 1-pyrenecarboxylic acid, 9-anthracenecarboxylic acid, and perylene-3,9-dicarboxylic acid─were chosen based on their desired properties before being incorporated into the construction of a K+-carrying gamma-cyclodextrin (γ-CD)-based metal-organic framework (CD-MOF-1) and γ-CD-containing hybrid f...

The substitution of three water molecules around trivalent chromium in CrBr3·6H2O with the tridentate 2,2':6',2''-terpyridine (tpy), N,N'-dimethyl-N,N'-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br3] complexes. Stepwise treatments with Ag(CF3SO3) and KCN under microwa...

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]helic...

The larger the ring, the better the chiroptical properties: A new family of highly distorted nanographenes is presented incorporating for the first time a nine-membered carbocycle. The nonagon-containing [5]helicene results in an extremely twisted helical moiety and provides to the final chiral PAHs with enhanced chiroptical properties. Abstract A...

Supramolecular interactions between molecules of the same or different nature determine to a great extent the degree of their applicability in many fields of science. To this regard, planar polycyclic aromatic hydrocarbons (PAHs) and their nanometric congeners, nanographenes (NGs), as well as positively curved ones, as for instance corannulene, hav...

The first enantioselective addition of alkyl BODIPY to Morita-Baylis-Hillman (MBH) carbonates is reported. This is the first reported enantioselective methodology using the methylene position of BODIPYs as nucleophiles. The reaction is efficiently catalyzed by cinchona alkaloids achieving high enantioselectivities and total diastereoselectivity. Th...

This work reports on the synthesis and characterization of five enantiomeric pairs of isostructural 3D metal-organic frameworks (MOFs) with the general formula {[Ln2(μ4-tar)2(μ-tar)(H2O)2]·xH2O}n [where Ln(III) = Tb (Tb-L and Tb-D), Dy (Dy-L and Dy-D), Ho (Ho-L and Ho-D), Er (Er-L and Er-D) and Tm (Tm-L and Tm-D); tar = tartrate (D- or L-) and x =...

Strukturdefekte sind ein möglicher Schlüssel für Fortschritte in der Nanographen‐Technologie. E. Maçôas, A. G. Campaña et al. zeigen in ihrem Forschungsartikel (DOI: 10.1002/ange.202000105), wie die Einführung eines Carbonyl‐substituierten heptagonalen Rings (Tropon) in ein Nanographenband die Effizienz der Upconversion‐Emission bei Zweiphotonenanr...

Understanding structural defects as potential advantages is the key for nanographene technology. In their Research Article (DOI: 10.1002/anie.202000105), E. Maçôas, A. G. Campaña, et al. show how the introduction of a carbonyl‐substituted heptagonal ring (tropone ring) into a nanographene ribbon increases the efficiency of upconverted emission by t...

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 prepare...

The advantage of defects: The effect of a tropone moiety on the nonlinear optical properties of ribbon-shaped nanographenes is unequivocally demonstrated. Curved edges created by the inclusion of heptagonal carbocycles enhance the two-photon absorption on graphene molecules. Abstract A new family of distorted ribbon-shaped nanographenes was design...

A unique rippled nanographene consisting of 52 fused rings is presented in which six out‐of‐plane motifs are fully fused into a triangular aromatic surface with a size of approximately 2.5 nm. Three units of an unprecedented fully lateral π‐extended octabenzo[5]helicene together with three units of saddle‐shaped heptagonal rings are combined in a s...

Ein chirales Nanographen aus vier anellierten Hexabenzocoronen‐Einheiten wurde synthetisiert. Sechs gebogene Einheiten wurden an eine dreieckige aromatische Oberfläche gebunden, wodurch drei Octabenzo[5]helicene und drei Sattelkanten entstanden. Die zwei diastereomeren Enantiomerenpaare emittieren im roten Spektralbereich und haben bemerkenswerte c...

Second-order data acquired using liquid chromatography coupled to a diode array detector were used to classify extra virgin olive oils samples according to their cultivars. The chromatographic fingerprints from the epoxidised fraction were obtained using normal-phase liquid chromatography. To reduce the data matrices two strategies were employed: (...

The controlled preparation of well-defined distorted nanographenes by a bottom-up approach based on organic synthesis permits the direct establishment of unprecedented structure–property relationships in carbon nanostructures. The simultaneous incorporation of various defects in nanographenes affords highly curved structures with novel or enhanced...

We report the synthesis and characterization of an enantiopure superhelicene nanographene constituted by two saddle‐shaped and one planar hexabenzocoronene (HBC) units arranged in a helicoidal shape. This is, to the best of our knowledge, the first undecabenzo[7]carbohelicene, i.e., the first fully π‐extended [7]helicene. Racemic resolution allowed...

We report the synthesis and characterization of an enantiopure superhelicene nanographene constituted by two saddle‐shaped and one planar hexabenzocoronene (HBC) units arranged in a helicoidal shape. This is, to the best of our knowledge, the first undecabenzo[7]carbohelicene, i.e., the first fully π‐extended [7]helicene. Racemic resolution allowed...

Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects...

The term coupling-and-decoupling (CAD) chemistry refers to applications in which efficient bond formation and subsequent cleavage between two moieties is required. Within this context, the scope of the vinyl sulfonate (VSO) group as an effi- cient tool for CAD chemistry is reported. The cou- pling step relies on the click features of the Michael- t...

The front cover image illustrates the new vinyl sulfonate-based “click” Coupling-and-Decoupling methodology by Victor Blanco, Francisco Santoyo-Gonzalez and co-workers. The coupling step relies on the click Michael-type addition of nucleophiles to vinyl sulfonates, while the decoupling involves the cleavage of the resulting sulfonate adducts either...

Highly distorted polycyclic aromatic hydrocarbons (PAHs) are predicted to be attractive goals in nanoscience owing to the new properties they can exhibit. We have shown that a variety of functionalized distorted heptagon-containing nanographenes can be easily prepared from simple building blocks by a sequence of Co-catalyzed cyclotrimerization and...