High spin (S = 1) organic diradicals may offer enhanced properties with respect to several emerging technologies, but typically exhibit low singlet triplet energy gaps and possess limited thermal stability. We report triplet ground state diradical 2 with a large singlet-triplet energy gap, ΔE ST ≥ 1.7 kcal mol −1 , leading to nearly exclusive population of triplet ground state at room temperature, and good thermal stability with onset of decomposition at ~160 °C under inert atmosphere. Magnetic properties of 2 and the previously prepared diradical 1 are characterized by SQUID magnetometry of polycrystalline powders, in polystyrene glass, and in other matrices. Polycrystalline diradical 2 forms a novel one-dimensional (1D) spin-1 (S = 1) chain of organic radicals with intrachain antiferromagnetic coupling of J′/k = −14 K, which is associated with the N•••N and N•••O intermolecular contacts. The intrachain antiferromagnetic coupling in 2 is by far strongest among all studied 1D S = 1 chains of organic radicals, which also makes 1D S = 1 chains *

Organic molecules with high-spin ground states, besides being fundamentally interesting, possess numerous potential applications in diverse fields such organic magnetism, MRI contrast agents, and spintronics. Such molecules, once thought to exist only as highly reactive intermediates, can be rationally designed to have adequate stability for organic synthesis and characterization. This Synopsis provides an overview of the factors that lead to high-spin ground states as well as recent progress in the design and synthesis of high-spin organic molecules.

Triplet ground-state organic molecules are interesting with respect to several emerging technologies but typically exhibit limited stability. We report two organic diradicals, one of which possesses a triplet ground state (2J/kB = 234 ± 36 K) and robust stability at elevated temperatures. We are able to sublime this high-spin diradical under high vacuum at 140 °C with no significant decomposition.

Organic radicals are fascinating materials because of their unique properties, which make them suitable for a variety of applications. Their synthesis may be challenging, and big efforts have focused on chemical stability. However, introducing a new material in electronics not only requires chemically stable molecules but also stable monolayers and thin films in view of their use in devices. In this work, we have investigated the thin films of a derivative of the Blatter radical that was synthesized bearing in mind the thermodynamic factors that govern thin film stability. We have proved our concept by investigating the electronic structure, the paramagnetic character, and stability of the obtained films under UHV and ambient conditions by in situ X-ray photoelectron spectroscopy, ex situ atomic force microscopy, and electron paramagnetic resonance spectroscopy.

Nitroxides occupy a privileged position among plausible metal-free magnetic resonance imaging (MRI) contrast agents (CAs) due to their inherently low-toxicity profiles; nevertheless, their translational development has been hindered by a lack of appropriate contrast sensitivity. Nanostructured materials with high nitroxide densities, where each individual nitroxide within a macromolecular construct contributes to the image contrast, could address this limitation, but the synthesis of such materials remains challenging. Here, we report a modular and scalable synthetic

The polymerization of functional monomers provides direct access to functional polymers without need for postpolymerization modification; however, monomer synthesis can become a bottleneck of this approach. New methods that enable rapid installation of functionality into monomers for living polymerization are valuable. Here, we report the three-step convergent synthesis (two-step longest linear sequence) of a divalent exo-norbornene imide capable of efficient coupling with various nucleophiles and azides to produce diversely functionalized branched macromonomers optimized for ring-opening metathesis polymerization (ROMP). In addition, we describe an efficient iterative procedure for the synthesis of tri-and tetra-valent branched macromonomers. We demonstrate the use of these branched macromonomers for the synthesis of Janus bottlebrush block copolymers as well as for the generation of bottlebrush polymers with up to three conjugated small molecules per repeat unit. This work significantly expands the scalability and diversity of nanostructured macromolecules accessible via ROMP.

By using a multidisciplinary and multitechnique approach, we have addressed the issue of attaching a molecular quantum bit to a real surface. First, we demonstrate that an organic derivative of the pyrene−Blatter radical is a potential molecular quantum bit. Our study of the interface of the pyrene−Blatter radical with a copper-based surface reveals that the spin of the interface layer is not canceled by the interaction with the surface and that the Blatter radical is resistant in presence of molecular water. Although the measured pyrene−Blatter derivative quantum coherence time is not the highest value known, this molecule is known as a "super stable" radical. Conversely, other potential qubits show poor thin film stability upon air exposure. Therefore, we discuss strategies to make molecular systems candidates as qubits competitive, bridging the gap between potential and real applications.

The synthesis of functional poly(2-alkyl-2-oxazoline) (PAOx) copolymers with complex nanoarchitectures using a graft-through ring-opening metathesis polymerization (ROMP) approach is described. First, well-defined norbornene-terminated poly(2-ethyl-2-oxazoline) (PEtOx) macromonomers (MM) were prepared by cationic ringopening polymerization. ROMP of these MMs produced bottlebrush copolymers with PEtOx side chains. In addition, PEtOx-based branched MMs bearing a terminal alkyne group were prepared and conjugated to an azidecontaining bis-spirocyclohexyl nitroxide via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). ROMP of this branched MM, followed by in situ cross-linking, provided PEtOx-based brush-arm star polymers (BASPs) with nitroxide radicals localized at the core-shell interface. These PEtOx-*