Lawrence T. (Larry) Scott

#PiSky L-region APEX

Chiral Nanohoops as an Efficient Spin Polarization System #PiSky

Creating and Manipulating π-Extended Quintulene on Surfaces - ChemistryViews A curved nitrogen-doped nanocarbon synthesized that can flip shape and trap a gold atom at its center

www.chemistryviews.org/creating-and... #PiSky

On-Surface Synthesis of a Nitrogen-Doped Curved Cycloarene: π-Extended Pentaazaquintulene and Its Gold Complex | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

Precise Synthesis of Pyrene-Based Molecular Nanocarbons Driven by Dehydro-Diels–Alder Reactions Molecular nanocarbons are critical bridges between small polycyclic aromatic hydrocarbons and extended graphene lattices, driving advances across materials science, optoelectronics, and quantum technologies. However, the atomically precise synthesis of such systems, particularly those featuring K-region and cove-type topologies, remains an enduring challenge. Here, we present a de novo modular strategy that overcomes this constraint by directing K-region growth via annulation of preorganized aryl acetylnaphthalene precursors with acetylenedicarboxylate. The strategy mirrors the hierarchical construction of pyrene by formally inserting naphthalene fragments into spatially defined molecular scaffolds. This method integrates Suzuki–Miyaura coupling with a Zn(OTf)2-catalyzed cascade comprising Friedel–Crafts alkylation, dehydro-Diels–Alder cycloaddition, and dehydrogenative aromatization. The platform affords structurally diverse pyrene-based molecular nanocarbons with programmable control over topology and dimensionality, spanning linear, contorted, and three-dimensional π-architectures. These results establish a generalizable blueprint for bottom-up synthesis of complex carbon-rich architectures with atomic precision.

pubs.acs.org/doi/10.1021/... #PiSky

Size and Geometry Impact the Chiroptical Properties of Double Nanohoops Conjugated nanohoops have attracted much attention in recent years due to their unique optoelectronic properties. A more complex geometry, in which two nanohoops are covalently linked to form a so-cal...

Size and Geometry Impact the Chiroptical Properties of Double Nanohoops | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

(Chiro)optical Properties of π-Extended Spiro-Double Carbo[7]helicene Helical nanographenes are a fascinating class of π-extended chiral nanocarbons, where structural helicity imparts intrinsic chirality and unique optoelectronic properties to the rigid carbon framework. In this work, we synthesized a hexa-peri-hexabenzocoronene-based π-extended spiro-double carbo[7]helicene. The helical distortion of the structure was unambiguously confirmed by X-ray crystallography. The optical properties were explored through UV–Vis absorption, fluorescence, and phosphorescence measurements, complemented by density functional theory (DFT) calculations. Remarkably, the π-extended spiro-double carbo[7]helicene exhibited thermally activated delayed fluorescence (TADF) at room temperature and phosphorescence at low temperatures. Chiral HPLC successfully resolved the enantiomers into three fractions: (PP), (MM), and the meso forms (PM)/(MP), and chiroptical studies of the pure enantiomers revealed a moderately high glum value of 1.58 × 10–3. Finally, the origin of the observed dissymmetry factors was rationalized by analyzing the transition electric dipole moments (TEDM) and transition magnetic dipole moments (TMDM) derived from time-dependent density functional theory (TD-DFT) calculations.

(Chiro)optical Properties of π-Extended Spiro-Double Carbo[7]helicene | The Journal of Physical Chemistry Letters pubs.acs.org/doi/abs/10.1... #PiSky

[n]Helicenes with Red to Near‐Infrared (NIR) Emissions and Circularly Polarized Luminescence Helicenes, chiral molecules with helical structures, are promising candidates for circularly polarized luminescence (CPL) materials. This review summarizes recent advances in red-to-NIR CPL-active he...

[n]Helicenes with Red to Near‐Infrared (NIR) Emissions and Circularly Polarized Luminescence - Li - Chemistry – A European Journal - Wiley Online Library chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/... #PiSky

A Persistent Open-Shell m-QDM-Type Diindenoanthracene Diradicaloid with a Large Diradical Character Indenofluorenes (IFs) have received great interest owing to their intrinsic antiaromaticity, open-shell diradical character, and narrow band gaps. Herein, we report the synthesis and comprehensive cha...

A Persistent Open-Shell m-QDM-Type Diindenoanthracene Diradicaloid with a Large Diradical Character pubs.acs.org/doi/10.1021/... #PiSky

Symmetry‐Breaking in Carbon Nanohoops Enables Room‐Temperature Ternary Single‐Molecule Switching Three pyrene-embedded nanohoops with distinct molecular symmetries were synthesized. Symmetry engineering discretizes the tunneling pathways, yielding three stable conductance states at room temperat...

Symmetry‐Breaking in Carbon Nanohoops Enables Room‐Temperature Ternary Single‐Molecule Switching - Chang - Angewandte Chemie International Edition - Wiley Online Library onlinelibrary.wiley.com/doi/10.1002/... #PiSky

chemrxiv.org/engage/chemr... #PiSky

Aromaticity and through-space electronic coupling in [2]catenanes #PiSky

Oxygen-doped carbon quantum rings #PiSky

Computational method can calculate forces between large molecules with unprecedented accuracy A puzzle in theoretical chemistry has been solved at TU Wien: A new computational method now makes it possible to calculate the forces between large molecules with unprecedented accuracy.

phys.org/news/2025-10... #PiSky

Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless Dye Extended π-conjugated systems are often insoluble, and their aggregation manner greatly affects their absorption spectra. This study produced a planar, soluble, and nonaggregated hexarylene-bisimide (HB) with appropriate substituents. The single-crystal X-ray structure of HB confirmed the planar molecular structure with small twist angles and the dimerization behavior of HB in the solid state. The concentration-dependent 1H NMR experiments in CDCl3 indicated that the association constant Kdimer is 4.6 × 103 M–1 at 298 K and ΔGdimer (298 K) = −20.8 kJ mol–1. The longest absorption of HB at the monomeric state exhibits a sharp and intense peak at 921 nm (ε = 230,000 M–1 cm–1, full width at half-maximum = 718 cm–1) in toluene. 75% of the absorption of HB above 400 nm appears in the near-infrared region, thus giving a practically colorless solution. Magnetic circular dichroism spectra of a series of oligorylene-bisimides reveal the predominant contribution of the linear polyene-like conjugation over the annulene-like conjugation for larger [n]oligorylene-bisimides.

Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless Dye | The Journal of Organic Chemistry pubs.acs.org/doi/10.1021/... #PiSky

Synthesis and Characterization of a π-Extended Clar’s Goblet Concealed non-Kekulé polybenzenoid hydrocarbons have no sublattice imbalance yet cannot be assigned a classical Kekulé structure, leading to an open-shell ground state with potential applications in o...

Synthesis and Characterization of a π-Extended Clar’s Goblet | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

N‐Doped Nonalternant Molecular Bowl/Saddle Hybrids N-Doped molecular bowl/saddle hybrids were developed via core-expansion synthetic strategy. Owing to the structural features containing both positive and negative curvatures, these molecules exhibit ....

N‐Doped Nonalternant Molecular Bowl/Saddle Hybrids - Qiu - Angewandte Chemie - Wiley Online Library onlinelibrary.wiley.com/doi/10.1002/... #PiSky

Congratulations, Harry! Another home run! Synthesis of triple stranded porphyrin nanobelts | Science www.science.org/doi/10.1126/... #PiSky

Epic! Congratulations, Mike.

Fused Octapyrrolyl Cyclooctatetraene with Large NIR-II Faraday Rotation The increased mechanical flexibility, solution processability, ease of fabrication, and high Verdet constants have made organic Faraday rotators a promising alternative to conventional inorganic magneto-optical (MO) materials. Despite this, organic Faraday rotators have not been developed to address near-infrared (NIR) MO applications, limiting their device applications. Here, we describe a three-step synthesis and MO characterization of a fused octapyrrolyl cyclooctatetraene (FOPCOT) which exhibits a record high Verdet constant of a small molecule in the NIR-II region. Notably, the cyclooctatetraene core is constructed in a three-step one-pot reaction whereby a N,N′-dipyrrolyl acetylene is generated and immediately reacted with Rosenthal’s complex to produce the corresponding zirconacycle intermediate in situ. The cascade is completed with a copper-mediated transmetalation that reductively eliminates to yield the octapyrrolyl cyclooctatetraene. This transformation offers a distinct alternative to conventional methods for pyrrole incorporation into polycyclic aromatic hydrocarbons. Stoichiometric oxidation with AgPF6 affords the oxidized analogues FOPCOT•+ and FOPCOT2+, which display strong optical absorptions at 1743 and 1198 nm, respectively. Magnetic circular dichroism study on spin-coated thin films of FOPCOT2+ yielded a maximum Verdet constant of −2.5 × 105 deg T–1 m–1 at 1224 nm.

Fused Octapyrrolyl Cyclooctatetraene with Large NIR-II Faraday Rotation | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

Stable Cycloparaphenylene Diradical Dications with Macrocyclic Aromaticity The first crystalline diradical dication [9]CPP2•2+ was successfully synthesized via an oxidation reaction under the support of weakly coordinating anion. Both experimental and theoretical analyses c...

Stable Cycloparaphenylene Diradical Dications with Macrocyclic Aromaticity onlinelibrary.wiley.com/doi/10.1002/... #PiSky

Triplet Spin Delocalization and Temperature Dependence for Adiabatic and Non-Adiabatic Z–E Isomerization Pathways in Azoarenes Photoswitching molecules like the azoarenes have myriad potential applications, ranging from energy storage to targeted drug delivery. Upon irradiation, azoarenes convert from an E-form to a Z-form. T...

Now in @jacs.acspublications.org Sharing Francisco’s new work on modulating the thermal isomerization mechanisms of photoswitching azoarenes. pubs.acs.org/doi/full/10....

Giant aromatic macrocycle #PiSky

BODIPY Antiaromatic Nanographenes chemrxiv.org/engage/chemr... #PiSky

Expanding Chemistry of Expanded Helicenes This review presents recent advances in the chemistry of expanded helicenes, defined as helicenes containing linearly fused benzene rings, as novel aromatic compounds. This review begins with a summa...

Helicenes get bigger chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/... #PiSky

Solution-phase stabilization of a cyclocarbon by catenane formation Cyclo[N]carbons, molecular rings consisting solely of N carbon atoms, have previously been studied in the gas phase and on surfaces at cryogenic temperatures, but they are generally considered too rea...

Our democratically elected #paperofthemonth is Anderson's solution-phase stabilization of a cyclocarbon through catenane formation. Congrats to the Oxford team on this milestone!
doi.org/10.1126/scie...

Congratulations, Ken!

New Account out 🎉: Cyclooctynes as versatile platforms for arene-annulated 8-membered rings - covering Diels–Alder strategies, key dienes/dienophiles, and future applications in materials & biology.

A bioactive nanocarbon that targets cross-species protein–protein interactions #PiSky

Fluoride-induced sign inversion of circularly polarized luminescence of B,N-thia[8]helicene #PiSky