Lawrence T. (Larry) Scott

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

Fluoranthene-Containing Distorted Nanographenes Exhibiting Two-Photon Absorption Response Two distorted nanographenes combining helicenes and a fluoranthene unit within their polycyclic scaffolds were synthesized. Their structural and electronic properties were elucidated by various spectr...

Delighted to share the work of John Bergner about the influence of fluoranthene in the TPA response of ribbon-shape nanographenes! 😊 Huge congratulation to the team at Kivala Group, Campaña Lab and Ermelinda Maçôas. Beautiful work! 👏
doi.org/10.1021/acs.... #PiSky

Achieving High‐Brightness NIR‐II Emission: Molecular Locking and Wrapping Strategies in Fluorescent Material Design for in Vivo Bioimaging This study presents a molecular design strategy for bright NIR-II fluorophores by addressing fluorescence quenching and low absorption in aggregates. Through structural optimization of donor-acceptor...

Achieving High‐Brightness NIR‐II Emission: Molecular Locking and Wrapping Strategies in Fluorescent Material Design for in Vivo Bioimaging - Congratulations, Ken! advanced.onlinelibrary.wiley.com/doi/10.1002/... #PiSky

Indeno[2,1‐c]fluorene Quasi[8]circulenes Through Intramolecular Cyclization A new class of curved, chiral polycyclic aromatic hydrocarbon emerges from the fusion of indeno[2,1-c]fluorene and quasi[8]circulene motifs. These redox-active, antiaromatic scaffolds offer great syn...

onlinelibrary.wiley.com/doi/10.1002/... #PiSky

Modulation of Koelsch Radical Stability and Aromaticity through Nonhexagonal Ring Fusion The synthesis and properties of a fused Koelsch radical derivative incorporating a seven-membered ring are described. The strategic incorporation of a heptagon into the extended π-system was hypothesi...

Modulation of Koelsch Radical Stability and Aromaticity through Nonhexagonal Ring Fusion | Organic Letters pubs.acs.org/doi/10.1021/... #PiSky

Saturated Carbazole-Embedded BN-Aromatic Systems as Narrowband Sky-Blue Emitters pubs.rsc.org/en/content/a... #PiSky

Pushing Carbon Nanohoops to Dark Green by Inserting BODIPY Dye Into Cycloparaphenylene Scaffolds We synthesized a series of carbon nanohoops, [n]CPP-BODIPY (n = 6, 7, and 9), by embedding boron dipyrromethene (BODIPY) dye into cycloparaphenylene scaffolds. Due to the unique size effect and intra...

Pushing Carbon Nanohoops to Dark Green by Inserting BODIPY Dye Into Cycloparaphenylene Scaffolds - Yuan - Chemistry – An Asian Journal - Wiley Online Library #PiSky aces.onlinelibrary.wiley.com/doi/10.1002/...

From Aqua Green to Deep Red in One Step: Targeted Design of a Highly Luminescent Phosphacyclic Vat Orange 3 Dye #PiSky

From Aqua Green to Deep Red in One Step: Targeted Design of a Highly Luminescent Phosphacyclic Vat Orange 3 Dye Silver-mediated phosphacyclic ring expansion with strategic placement of phosphorus and dimethyl acetylenedicarboxylate (DMAD) on Vat Orange 3 was carried out. The target compounds possess narrow HOMO...

Reza’s latest work is hot off the press!
Happy to contribute to the conjugated materials special issue in Organic Letters #ChemSky #PiSky pubs.acs.org/doi/10.1021/...

Electrophotocatalytic decarbonylative [4+2] cyclization of indenones #PiSky

Benzene at 200 Celebrating the molecule that changed the world

Benzene at 200 www.chemistryworld.com/opinion/benz... #PiSky

Hearty congratulations, Marina!

Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their perfor...

Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

C2-Symmetric Perylene-Embedded Double [5]Helicenes High quantum yields and dissymmetry factors are key to enhancing the chiroptical properties of [n]helicene-functionalized polycyclic aromatic hydrocarbons for the development of circularly polarized materials. In a two-step synthesis, a C2-symmetric perylene-embedded double [5]helicene was obtained through Suzuki–Miyaura cross-coupling and base-catalyzed condensation. With a configurational stability of 23 kcal mol–1, the short-lived enantiomers were separated using chiral HPLC. Compared to pristine [5]helicene, the compound shows enhanced (chir)optical properties with a quantum yield of 0.7, a gabs of up to 8.8 × 10–3, and a glum of 0.7 × 10–3.

C2-Symmetric Perylene-Embedded Double [5]Helicenes | Organic Letters pubs.acs.org/doi/full/10.... #PiSky

BNB-Modified Perylene, Terrylene, and Quaterrylene Diimides: Introduction of the π-Accepting and Aggregation-Suppressing Diborinic Imide Group in Rylene Dyes Rylene diimides are among the most intensively researched classes of functional organic dyes. They are characterized by outstanding photoabsorption and -emission properties in combination with excellent photostability and thermal stability. Due to strong intermolecular π–π interactions, the larger, peri-extended rylene diimides, in particular, require the complex attachment of solubilizing substituents to enable their handling and processing in the solution phase. Herein, we introduce the diborinic imide functional group as a substitute for the commonly used dicarboximide moiety at the peri-termini of rylenes, thus leading to a new class of well-soluble rylene dyes with excellent optoelectronic properties. We synthesized borinic diimides of perylene (PDBI 5), terrylene (TDBI 7), and quaterrylene (QDBI 9) starting from a BNB-modified phenalenyl (1). These compounds show progressively bathochromically shifted absorption and emission characteristics with increasing system size, with fluorescence quantum yields up to ΦF = 0.92 for 5, and extended NIR (near-infrared) emission for 9. Single-crystal X-ray diffraction (XRD) studies reveal modified molecular packing in the solid state, pointing to a reduced tendency to aggregation. The new compounds undergo two reversible successive reductions, which were monitored by UV–vis–NIR spectroelectrochemistry. We performed the chemical reduction of 5 to obtain the potassium salts of the mono- and the dianion, K[5] and K2[5], respectively. Both the dianion and, in contrast to common rylene diimide dyes, also the monoanion show fluorescence emission, which extends into the NIR region. Quantum chemical ACID and 2D-NICSZZ calculations reveal a transition from mainly local aromaticity to global aromaticity upon reduction.

BNB-Modified Perylene, Terrylene, and Quaterrylene Diimides: Introduction of the π-Accepting and Aggregation-Suppressing Diborinic Imide Group in Rylene Dyes | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/... #PiSky

Synthesis of Azuleno[1,2,3-cd]phenalene and Its π-Extended Buckybowl Derivative Azulene-fused molecular carbons have sparked intense research interest in recent years. Herein, we report a facile three-step synthesis of azuleno[1,2,3-cd]phenalene (AzPn), a fused system combining a...

Synthesis of Azuleno[1,2,3-cd]phenalene and Its π-Extended Buckybowl Derivative | Organic Letters pubs.acs.org/doi/10.1021/... #PiSky

Intrinsic Luminescence of Pure Organic Mono- and Di-Radicals in Aggregated States - ChemistryViews Strategy enables efficient organic radical luminescence in solids by suppressing harmful interactions, aiding solid-state lighting

Strategy enables efficient organic radical luminescence in solids by suppressing harmful interactions, aiding solid-state lighting
www.chemistryviews.org/intrinsic-lu...

Very cool, Ken!

August issue now online!

www.nature.com/natsynth/vol...

#Chemsky