☆ 4.8 Review

Heteroatom-Based Diradical(oid)s

CHEMICAL REVIEWS (2023)

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Article Chemistry, Multidisciplinary

An isolable germylyne radical with a one-coordinate germanium atom

Dongmin Wang et al.

Summary: In this study, the isolation, characterization and reactivity of a crystalline germylyne radical using a sterically hindered hydrindacene ligand was reported. The resulting germylyne radical features a one-coordinate germanium atom and exhibits a doublet ground state.

NATURE CHEMISTRY (2023)

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Article Chemistry, Organic

Synthesis of mono-nitroxides and of bis-nitroxides with varying electronic through-bond communication

Angeliki Giannoulis et al.

Summary: Nitroxides, a unique class of persistent radicals, have a wide range of applications, from spin probes to polarizing agents. This study focuses on the synthesis of pyrroline-based nitroxide radicals and compares two possible synthetic routes for forming two key intermediates. The synthesized compounds were characterized using X-ray crystallography and their electronic communication was quantified using Continuous Wave Electron Paramagnetic Resonance (CW-EPR). This research expands the repertoire of mono- and bis-nitroxides and paves the way for studying quantum coherence effects and using them as polarizing agents.

ORGANIC & BIOMOLECULAR CHEMISTRY (2023)

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Article Chemistry, Inorganic & Nuclear

The Sequence Makes the Difference: On the Reaction of Phosphorus-centered Biradical [•P(μ-N-tBuPh3C)2P•] with Tolan

Sebastian Berthold et al.

Summary: By reducing a cyclic dichlorophosphane using magnesium, a biradical [P(center dot)(mu-N-(Ph3C)-Ph-tBu)(2)P(center dot)] (6T) can be obtained. When this biradical reacts with alkynes, such as tolan, the addition product [P(mu-N-(Ph3C)-Ph-tBu)(2)P(Ph-C=C-Ph)] (7), a [2.1.1] bicyclic species, is formed. However, if the reduction process is carried out in the presence of tolan, a different reaction occurs, resulting in a magnesium(II) double salt with a novel tolan-stabilized [(PhC=CPh)P-N-P(PhC=CPh)](-) anion.

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE (2023)

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Article Chemistry, Multidisciplinary

Redox-Active Lewis Pairs Yield Diradicaloids and Enable Modular Control of the Diradical Character

Rezisha Maskey et al.

Summary: Stable metal-free diradicaloids with modifiable nitrogen-containing frameworks can be synthesized through Lewis acid-base pair formation. This method allows for the one-step synthesis of diradicaloids with rationally adjustable diradical character, presenting great potential for various applications.

CHEMISTRY-A EUROPEAN JOURNAL (2023)

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Article Chemistry, Multidisciplinary

Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum

Dongmin Wang et al.

Summary: Here, the synthesis and characterization of a neutral monosubstituted Sn(I) radical (2) supported by a sterically hindered hydrindacene ligand is reported, which represents the first tin analogue of a free carbyne. The unique electronic structure of 2, with a sole Sn-C sigma bond, results in a S = 1/2 ground state with two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum. 2 exhibits reactivity towards N-heterocyclic carbene, benzophenone, diphenyl diselenide, and p-benzoquinone, forming Sn-S and Sn-O bonds.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Article Chemistry, Multidisciplinary

Rational Design of Persistent Phosphorus-Centered Singlet Tetraradicals and Their Use in Small-Molecule Activation

Edgar Zander et al.

Summary: In this study, a persistent phosphorus-centered tetraradical was isolated and found to be capable of activating small molecules. Quantum mechanical calculations were used to compare its properties and aromaticity with other known tetraradicals and biradicals.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Article Multidisciplinary Sciences

Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response

Yue Pang et al.

Summary: In this work, the synthesis and characterization of a monocoordinate bismuthinidene compound with a rigid and bulky ligand were reported. Despite showing diamagnetic properties in all magnetic measurements, multiconfigurational quantum chemical calculations revealed that the compound's ground state is dominated by a spin triplet. The apparent diamagnetism is explained by an extremely large spin-orbit coupling-induced positive zero-field splitting.

SCIENCE (2023)

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Article Chemistry, Multidisciplinary

A triplet stibinidene

Mengyuan Wu et al.

Chem (2023)

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Article Chemistry, Multidisciplinary

Isolation of an Annulated 1,4-Distibabenzene Diradicaloid

Henric Steffenfauseweh et al.

Summary: A bordeaux-red solid compound based on an anionic dicarbene (ADC) with a central six-membered C4Sb2 ring is reported. The compound undergoes 2 e-oxidation to form a brick-red solid with unpaired electrons and lone pairs. The diradical character of the compound is calculated to be 36-39% according to different methods.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

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Article Chemistry, Multidisciplinary

Captodative Effect Facilitates the Excitation in Diboron Molecule (CAAC)2B2(SH)2

Huaiyu Zhang et al.

Summary: In the past two decades, boron compounds have attracted increasing attention due to their extraordinary versatility in chemical reactions and applications. One of the notable advancements is the unprecedented preparation of unsaturated boron species. This study focuses on the role of thiol substituents in (CAAC)2B2(SR)2 and identifies the co-planarity of thiol groups and the captodative effect as the reason for its 90 degrees-twisted diradical form. Computational analyses reveal two forces contributing to the pi electron movements, including the push effect of lone pairs on sulfur atoms and the pi electron delocalization within each (CAAC)B(SR) fragment.

CHEMISTRY-A EUROPEAN JOURNAL (2023)

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Review Chemistry, Multidisciplinary

Tuning the Electronic Properties of Main-Group Species by N-Heterocyclic Vinyl (NHV) Scaffolds

Rajendra S. Ghadwal

Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.

ACCOUNTS OF CHEMICAL RESEARCH (2022)

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Article Chemistry, Multidisciplinary

Tuning Diradical Properties of Boron-Containing π-Systems by Structural Isomerism

Xinyu Tian et al.

Summary: Tuning the diradical character and properties of organic diradicaloids can be achieved through precise borylation reactions. The synthesized B-containing polycyclic hydrocarbon exhibits distinctive electronic structures and properties compared to its isomeric molecule. Moreover, it shows smaller diradical character and enhanced Lewis acidity, which can further enhance its diradical performance through Lewis coordination.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Article Chemistry, Multidisciplinary

A Phosphorus-Based Pacman Dication Generated by Cooperative Self-Activation of a Pacman Phosphane

Liesa Eickhoff et al.

Summary: The formal coordination of phosphorus(III) was achieved by reacting a calix[4]pyrrole Schiff base ligand with PCl3 under basic conditions, resulting in a Pacman conformation reaction product. The spatial neighborhood of the two phosphorus atoms enables cooperative reactions, demonstrated by the chloride abstraction reaction with AgOTf to yield two embedded phosphorus(III) monocations.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Article Chemistry, Inorganic & Nuclear

Valence Tautomerism of p-Block Element Compounds - An Eligible Phenomenon for Main Group Catalysis?

Lutz Greb

Summary: Valence tautomerism has a significant impact on transition metal chemistry, and its applicability to p-block elements is still at an early stage. However, considering the substantial disparity in the properties of p-block elements in different redox states, this concept may offer a valid extension for future developments in main group catalysis.

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (2022)

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Review Chemistry, Inorganic & Nuclear

Bicyclic and tricyclic phosphanes with p-block substituents

Jonas Bresien et al.

Summary: This review summarizes the experimental and structural knowledge on polycyclic phosphanes, with a focus on bicyclic and tricyclic phosphanes, which have been the most studied in the last 25 years and exhibit the greatest diversity in terms of constitutional isomerism and structural motifs. Only polycyclic phosphanes with p-block substituents at all free valences are discussed.

REVIEWS IN INORGANIC CHEMISTRY (2022)

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Article Chemistry, Multidisciplinary

Synthesis, Structure and Electronic Properties of a Stable π-Type 3-Electron-2-Center-Bonded Species: A Silicon Analogue of a Bicyclo[1.1.0]butane Radical Anion

Taichi Koike et al.

Summary: Here, we report the synthesis and characterization of a stable pi-type 3e-2c-bonded species. This compound exhibits a unique bonding motif and provides a new approach for constructing pi-electron systems.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Isolation of an Arsenic Diradicaloid with a Cyclic C2As2-Core

Henric Steffenfauseweh et al.

Summary: In this study, the synthesis, characterization, and reactivity of the first cyclic C2As2-diradicaloid compound were reported. The compound exhibits a planar C2As2 ring, is diamagnetic, and shows well resolved NMR signals.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Radical Reactivity of the Biradical [•P(μ-NTer)2P•] and Isolation of a Persistent Phosphorus-Cantered Monoradical [•P(μ-NTer)2P-Et]

Jan Rosenboom et al.

Summary: This study reports a new method for the activation of C-Br bonds in various bromoalkanes by a biradical, yielding 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes, and the mechanism of the reaction was confirmed as a stepwise radical reaction through spectroscopic methods and experimental data.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Article Chemistry, Multidisciplinary

Impact of Heterocycle Annulation on NIR Absorbance in Quinoid Thioacene Derivatives

Peng Hou et al.

Summary: This study presents the synthesis and characterization of a series of quinoid sulfur-containing imidazolyl-substituted heteroacenes. The optoelectronic and magnetic properties of these compounds were investigated using various spectroscopic techniques and quantum-chemical calculations, and compared to their benzo congeners.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Review Chemistry, Inorganic & Nuclear

Isolable silylenes and their diverse reactivity

Liliang Wang et al.

Summary: In the past three decades, a significant number of isolable silylenes have been synthesized and studied for their unique properties and characteristic reactions. This review focuses on the differences in properties and reactivities among stable silylenes and includes discussion of some extra-coordinated silylenes. The review covers substituent effects on Si-29 NMR chemical shift, UV-vis absorption maxima, MO properties, as well as diverse reactions and mechanisms of silylenes.

COORDINATION CHEMISTRY REVIEWS (2022)

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Article Chemistry, Multidisciplinary

Highly Strained Arene-Fused 1,2-Diborete Biradicaloid

Annalena Gaertner et al.

Summary: The stepwise reduction of a doubly cyclic alkyl(amino)carbene (CAAC)-stabilized 2,3-bis(dibromoboryl)naphthalene enables the isolation of various organic compounds, including boryl radicals, diborete, and cyclic bis(alkylidene)diboron dianion. The diborete exhibits biradical character and a highly strained structure.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Multidisciplinary

Bis(imidazolium)-1,3-diphosphete-diide: A Building Block for FeC2P2 Complexes and Clusters

Moritz Theodor Scharnhoelz et al.

Summary: In this study, a series of iron carbonyl complexes were synthesized and their electronic structures were analyzed. The complexes can be described as either electron precise or Wade-Mingos clusters.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

A Germapyramidane Switches Between 3D Cluster and 2D Cyclic Structures in Single-Electron Steps

Peter Coburger et al.

Summary: The reaction of imidazolium-substituted iphosphate-diide with GeCly dioxane and KBArF24 results in the formation of a rare dicationic spherical-aromatic nido-cluster. This complex undergoes two reversible one-electron reductions and rearranges to form 2D aromatic and planar structures. Oxidation of these planar species leads to the restoration of the 3D aromatic cluster.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Organic

A comparative study of biradicaloids as ligands in iron tetracarbonyl complexes

M. T. Scharnhoelz et al.

Summary: This article presents the isolation of two new iron tetracarbonyl complexes, [P(p-N-Ter)]2 and [P(p-C-IPr)]2, which exhibit biradicaloid structures with zwitterionic resonance in the complexes. Experimental evidence shows that their donor strength is comparable to N-heterocyclic carbenes (NHCs), with [P(p-C-IPr)]2 being slightly stronger than [P(p-N-Ter)]2. Additionally, an improved, scalable, and facile synthesis of both biradicaloids is described.

ARKIVOC (2022)

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Article Chemistry, Multidisciplinary

A bis-NHC-CAAC dimer derived dicationic diradical

Mithilesh Kumar Nayak et al.

Summary: In this study, a thermally stable dicationic diradical compound was synthesized and confirmed by EPR spectroscopy. The presence of the trans-1,4-cyclohexylene bridge was found to be essential for the successful isolation of this compound.

CHEMICAL SCIENCE (2022)

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Article Chemistry, Inorganic & Nuclear

Concerted addition of aldehydes to the singlet biradical [P(μ-NTer)]2

Jan Rosenboom et al.

Summary: This study demonstrated that the reaction of [P(mu-NTer)](2) with different aldehydes selectively yielded the corresponding [2.1.1]-bicyclic addition products, and it was shown to be a very rapid reaction. The mechanism of this addition reaction was found to be a concerted cycloaddition reaction with a very low activation barrier through theoretical investigation. Additionally, comparative studies revealed that all unsaturated reactants exhibited a similar reaction profile in their cycloaddition mechanisms.

DALTON TRANSACTIONS (2022)

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Article Chemistry, Multidisciplinary

A four-membered heterocyclic prevented biradical that can be described as a zwitterion or masked N-heterocyclic phosphinidene

Tim Suhrbier et al.

Summary: Heterocyclobutane-1,3-diyl compounds bridge the gap between organic and inorganic chemistry, and can be used for small molecule activation. They resemble conventional transition metal complexes and serve as cost-effective alternatives for future processes.

CELL REPORTS PHYSICAL SCIENCE (2022)

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Article Chemistry, Inorganic & Nuclear

A cyclic thioketone as biradical heterocyclopentane-1,3-diyl: synthesis, structure and activation chemistry

Henrik Beer et al.

Summary: This study describes the synthesis of a cyclic phospha-aza thiourea derivative through the reaction of a biradical with thiophosgene. The resulting cyclic thioketone, formed by reducing the phospha-aza thiourea derivative, exhibits unique properties as a biradical heterocyclopentane-1,3-diyl. Furthermore, this biradical can be converted to a housane species by light, triggering the formation of transannular P-P bonds.

INORGANIC CHEMISTRY FRONTIERS (2022)

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Article Chemistry, Multidisciplinary

Synthesis, Structure and Electronic Properties of a Stable pi-Type 3-Electron-2-Center-Bonded Species: A Silicon Analogue of a Bicydo[1.1.0]butane Radical Anion

Taichi Koike et al.

Summary: This study reports the synthesis of the first stable pi-type 3e-2c-bonded species, demonstrating a compound with an extremely long bridgehead Si-Si bond and strong near-IR absorption. DFT calculations revealed a pi-type bonding interaction between the two bridgehead silicon atoms, introducing a novel method for constructing pi-electron systems.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Azadiphosphaindane-1,3-diyls: A Class of Resonance-Stabilized Biradicals

Jonas Bresien et al.

Summary: The study revealed that the reaction of 1,2-bis(dichlorophosphino)benzene with sterically demanding primary amines resulted in the formation of a series of 1,3-dichloro-2-aza-1,3-diphosphaindanes, with the stability of the products depending on the size of substituent R. These products can be described as phosphorus-centered singlet biradical(oid)s, with oligomerization reactions occurring for some derivatives. Additionally, calculations showed that the biradical character in the products is comparable to known P-centered biradicals, and aromaticity was observed within the entire ring system.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

An Open-Shell Singlet SnI Diradical and H2 Splitting

Mahendra K. Sharma et al.

Summary: The text discusses the isolation of the first Sn-I diradical based on an anionic dicarbene scaffold, its molecular structure, and chemical reactivity with different compounds like PhSeSePh and MeOTf. The diradical exhibits a diatropic ring current and a small singlet-triplet energy gap, indicating its potential for further study in terms of its electronic properties.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Review Chemistry, Multidisciplinary

Pushing the Limits of Acene Chemistry: The Recent Surge of Large Acenes

Christina Toenshoff et al.

Summary: Acenes, a class of organic compounds with linearly fused benzene rings, have various applications. Recent advances in the study of acenes have provided deeper insight into their fundamental properties and electronic structure. The synthesis of larger acenes has been achieved through innovative methods and techniques.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

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Article Chemistry, Multidisciplinary

Twisting versus Delocalization in CAAC- and NHC-Stabilized Boron-Based Biradicals: The Roles of Sterics and Electronics

Paul Schmid et al.

Summary: This issue features the research work of Bernd Engels, Holger Braunschweig, Volker Engel and their coworkers at University of Wurzburg on bridged boron compounds, highlighting the fascinating relationships between their composition, geometrical structures, and electronic structures.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

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Article Chemistry, Multidisciplinary

Isolation of a Ge(I) Diradicaloid and Dihydrogen Splitting

Mahendra K. Sharma et al.

Summary: The cyclic Ge(I) compound 4 with a C4Ge2 framework exhibits diradical character, leading to the easy splitting of dihydrogen at room temperature to form the bis-hydridogermylene 5, which is elusive and difficult to capture.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Boron-Containing Organic Diradicaloids: Dynamically Modulating Singlet Diradical Character by Lewis Acid-Base Coordination

Jiaxiang Guo et al.

Summary: Organic diradicaloids have unique open-shell structures and properties, and introducing boron atoms into their structures can enhance their stability and lead to intriguing magnetic and optoelectronic properties. The B-containing organic diradicaloids reported in this article exhibit excellent ambient stability, open-shell singlet diradical structures, and unique Lewis acidity, demonstrating promising potential for novel applications in organic electronics and spintronics.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Stable Radical Cation and Dication of a 1,4-Disilabenzene

Yilin Chen et al.

Summary: In this study, compound 2 undergoes charge transfer reactions with various reagents, leading to the formation of stable radical cation and dication species of the 1,4-disilabenzene. Additionally, compound 2 also undergoes oxidative addition reactions with group 16 elements such as O, S, and Se.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Anionic Boron- and Carbon-Based Hetero-Diradicaloids Spanned by a p-Phenylene Bridge

Avijit Maiti et al.

Summary: This study presents the synthesis and characterization of anionic boron- and carbon-based Kekule diradicaloids connected by a p-phenylene bridge, which exhibit triplet state properties at room temperature. Additionally, the formation of an isolable diamino(4-diarylboryl-phenyl)methyl radical was observed during the synthesis process.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Review Chemistry, Multidisciplinary

Persistent and Stable Organic Radicals: Design, Synthesis, and Applications

Z. X. Chen et al.

Summary: The study of open-shell radicals has made significant progress, showing that persistent and stable radicals can be prepared through rational design and appropriate chemical constructions. These materials exhibit unique physicochemical properties that open up new possibilities in the fields of magnetism, electronics, optoelectronics, and biology.

CHEM (2021)

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Review Chemistry, Multidisciplinary

Open-Shell Graphene Fragments

Wangdong Zeng et al.

Summary: The electronic properties of finite-sized graphene fragments are strongly dependent on their topological structures, especially when they possess extended zigzag edges. Synthesis of open-shell molecules with unique magnetic activity is challenging, and can be predicted and analyzed using Clar's sextets and density functional theory. Their magnetic activity and quantum properties make them promising materials for carbon-based spintronic and quantum devices.

CHEM (2021)

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Article Chemistry, Multidisciplinary

Isolation of Neutral, Mono-, and Dicationic B2P2 Rings by Diphosphorus Addition to a Boron-Boron Triple Bond

Tobias Brueckner et al.

Summary: The study found that NHC-stabilised diboryne can undergo a high-yielding reaction with tetraethyldiphosphine at room temperature to form a B2P2 heterocycle, which can be oxidised to different ionic forms. With each oxidation step, the structure of the heterocycle changes, showing different forms.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Changing the Reactivity of Zero- and Mono-Valent Germanium with a Redox Non-Innocent Bis(silylenyl)carborane Ligand

Shenglai Yao et al.

Summary: Using a chelating C,C'-bis(silylenyl)-ortho-dicarborane ligand, a monoatomic zero-valent Ge complex was synthesized, showing different reactivities towards reductants and oxidants due to the redox non-innocent nature of the carborane scaffold. The reduction and oxidation of the Ge complex resulted in the formation of dianionic or dicationic bis(silylene)-supported Ge complexes with distinct properties.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Letter Multidisciplinary Sciences

Reply to: A double bond with weak σ- and strong π-interactions is still a double bond

Soichiro Kyushin et al.

NATURE COMMUNICATIONS (2021)

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Letter Multidisciplinary Sciences

A double bond with weak σ- and strong π-interactions is still a double bond

Cina Foroutan-Nejad

NATURE COMMUNICATIONS (2021)

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Article Chemistry, Inorganic & Nuclear

Insights into the naphthalenide-driven synthesis and reactivity of zerovalent iron nanoparticles

Andreas Reiss et al.

Summary: The chemical and thermal stability of alkali metal naphthalenides as powerful reducing agents was examined, with [LiNaph] solutions in THF at low temperature found to be most stable and used to prepare reactive zerovalent iron nanoparticles. The decomposition may be related to a reductive polymerization of the solvent. The reactive Fe(0) nanoparticles obtained via [LiNaph]-driven reduction in liquid phase can be instantaneously reacted to give new compounds without remains of the initial reduction.

DALTON TRANSACTIONS (2021)

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Article Chemistry, Multidisciplinary

π-Conjugated species with an unsupported Si-Si π-bond obtained from direct π-extension

Takumi Nukazawa et al.

Summary: The compound with unsupported bridgehead Si-Si pi bond and ethynyl pi moieties was successfully synthesized, and effective pi conjugation between the unsupported Si-Si pi and ethynyl pi units was observed.

CHEMICAL COMMUNICATIONS (2021)

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Article Chemistry, Multidisciplinary

Isolation of 1,4-Diarsinine-1,4-diide and 1,4-Diarsinine Derivatives

Dennis Rottschafer et al.

Summary: The newly synthesized compound 5 is a red crystalline solid with an 8π electron C4As2 ring, exhibiting antiaromaticity. It can undergo oxidation reaction to form compound 6 with a 6π electron aromatic system.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Spin-labelled mechanically interlocked molecules as models for the interpretation of biradical EPR spectra

Lorenzo Gualandi et al.

Summary: Biradical spin probes can provide information about distances between molecules, but in supramolecular complexes, the shape of EPR spectra is influenced by the rate of exchange between different states, in addition to J. Thorough analysis of both J and rates of conformational interconversion is necessary when interpreting the spectra of biradicals employed as spin probes in solution.

CHEMICAL SCIENCE (2021)

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Review Chemistry, Multidisciplinary

Unconventional singlet fission materials

Tobias Ullrich et al.

Summary: Singlet fission is a photophysical downconversion pathway that transforms a singlet excitation into two triplet excited states, offering potential applications in solar energy conversion devices and other areas. While the mechanistic understanding of SF has evolved rapidly, the limited number of suitable SF-chromophores poses a challenge, necessitating the search for new SF materials.

CHEMICAL SOCIETY REVIEWS (2021)

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Article Chemistry, Physical

Photoisomerization of a phosphorus-based biradicaloid: ultrafast dynamics through a conical intersection

Tim Voelzer et al.

Summary: In this study, pump-probe spectroscopy was used to investigate the excited-state dynamics of the photoisomerization of [TerNID](2)CNDmp (2), revealing ultrafast de-excitation of the S-1 state through a conical intersection in agreement with computational predictions. The structural and electronic changes during the isomerization process were discussed to gain insight into the reaction pathway and the transformation of the biradicaloid to a closed-shell species.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2021)

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Article Chemistry, Multidisciplinary

Charge-Shift Bonding: A New and Unique Form of Bonding

Sason Shaik et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Review Nanoscience & Nanotechnology

Molecular magnetism: from chemical design to spin control in molecules, materials and devices

Eugenio Coronado

NATURE REVIEWS MATERIALS (2020)

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Article Chemistry, Multidisciplinary

N-Heterocyclic Carbene Stabilized Dicarbondiphosphides: Strong Neutral Four-Membered Heterocyclic 6π-Electron Donors

Zhongshu Li et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

CAAC-Based Thiele and Schlenk Hydrocarbons

Avijit Maiti et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Diindenoanthracene Diradicaloids Enable Rational, Incremental Tuning of Their Singlet-Triplet Energy Gaps

Justin J. Dressler et al.

CHEM (2020)

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Article Chemistry, Multidisciplinary

Equilibrium Formation of Stable All-Silicon Versions of 1,3-Cyclobutanediyl

Cem B. Yildiz et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Organic

Heterocyclopentanediyls vs Heterocyclopentadienes: A Question of Silyl Group Migration

Henrik Beer et al.

JOURNAL OF ORGANIC CHEMISTRY (2020)

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Article Chemistry, Multidisciplinary

An Isolable Tetrasilicon Analogue of a Planar Bicyclo[1.1.0]butane with π-Type Single-Bonding Character

Takumi Nukazawa et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Review Chemistry, Inorganic & Nuclear

An Update on Multiple Bonding between Heavier Main Group Elements: The Importance of Pauli Repulsion, Charge-Shift Character, and London Dispersion Force Effects

Philip P. Power

ORGANOMETALLICS (2020)

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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Article Chemistry, Multidisciplinary

Flexibility of N-Heterocyclic Carbene Ligands in Ruthenium Complexes Relevant to Olefin Metathesis and Their Impact in the First Coordination Sphere of the Metal

Francesco Ragone et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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Article Chemistry, Multidisciplinary

Synthesis of a Pentasilapropellane. Exploring the Nature of a Stretched Silicon-Silicon Bond in a Nonclassical Molecule

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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Article Chemistry, Multidisciplinary

Snapshots of the Al-Al sigma-Bond Formation Starting from {AlR2} Units: Experimental and Computational Observations

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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2009)

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Article Chemistry, Multidisciplinary

The regioselective photochemical rearrangement of α-[PNtBu]4

Henrike Bladt et al.

CHEMICAL COMMUNICATIONS (2009)

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Review Chemistry, Multidisciplinary

Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

Oliver Schuster et al.

CHEMICAL REVIEWS (2009)

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Article Chemistry, Multidisciplinary

Molecular Double-Bond Covalent Radii for Elements Li-E112

Pekka Pyykko et al.

CHEMISTRY-A EUROPEAN JOURNAL (2009)

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Article Chemistry, Inorganic & Nuclear

SambVca: A Web Application for the Calculation of the Buried Volume of N-Heterocyclic Carbene Ligands

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EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (2009)

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m-Terphenylphosphines: Synthesis, structures and coordination properties

Bryan Buster et al.

INORGANICA CHIMICA ACTA (2009)

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Article Chemistry, Physical

Consistent van der Waals Radii for the Whole Main Group

Manjeera Mantina et al.

JOURNAL OF PHYSICAL CHEMISTRY A (2009)

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Article Chemistry, Inorganic & Nuclear

Catenation of 1,3-Diphosphacyclobutane-2,4-diyl Units Having 2,4,6-Tri-tert-butylphenyl Protecting Groups and a P-sec-Butyl Group in the Ring

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ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE (2009)

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Article Chemistry, Multidisciplinary

Molecular magnesium(I) compounds: From curiosity to kudos

Matthias Westerhausen

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2008)

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Article Chemistry, Multidisciplinary

Generation of a triplet diradical from a donor-acceptor cross conjugate upon acid-induced electron transfer

Mats O. Sandberg et al.

CHEMICAL COMMUNICATIONS (2008)

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Review Chemistry, Multidisciplinary

CuH-catalyzed reactions

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CHEMICAL REVIEWS (2008)

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Editorial Material Chemistry, Multidisciplinary

Tetraazafulvalene: Organic sodium

Robert D. Richardson et al.

CHEMIE IN UNSERER ZEIT (2008)

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Reduction of Δ2-Isoxazolines to β-Hydroxy Ketones with Iron and Ammonium Chloride as Reducing Agent

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JOURNAL OF ORGANIC CHEMISTRY (2008)

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DIRECT SYNTHESIS OF 2,5-DIHALOSILOLES (2,5-Dibromo-1,1-dimethyl-3,4-diphenyl-1H-silole)

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ORGANIC SYNTHESES (2008)

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Substituent effects in formally quintuple-bonded ArCrCrAr compounds (Ar = terphenyl) and related species

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INORGANIC CHEMISTRY (2007)

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Article Multidisciplinary Sciences

Stable magnesium(I) compounds with Mg-Mg bonds

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Multiple bonding in heavier element compounds stabilized by bulky terphenyl Ligands

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INORGANIC CHEMISTRY (2007)

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Let's play with valence isomers: The influence of different main group elements on their relative stability

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BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN (2007)

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Steric effect: A quantitative description from density functional theory

Shubin Liu

JOURNAL OF CHEMICAL PHYSICS (2007)

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Synthesis and properties of air-stable 1,3-diphosphacyclobutane-2,4-diyls and the related compounds

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JOURNAL OF ORGANOMETALLIC CHEMISTRY (2007)

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Thermal valence isomerization of 2,3-diborata-1,4-diphosphoniabuta-1,3-dienes to bicyclo[1.1.0]butanes and cyclobutane-1,3-diyls

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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2007)

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Review Chemistry, Multidisciplinary

Chemistry of pnictogen(III)-nitrogen ring systems

Maravanji S. Balakrishna et al.

CHEMICAL SOCIETY REVIEWS (2007)

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1,3-DICHLOROACETONE AS A CYCLOPROPANONE EQUIVALENT: 5-OXASPIRO[3.4]OCTAN-1-ONE

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ORGANIC SYNTHESES (2007)

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Review Chemistry, Inorganic & Nuclear

Stereoelectronic parameters associated with N-heterocyclic carbene (NHC) ligands: A quest for understanding

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COORDINATION CHEMISTRY REVIEWS (2007)

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Review Chemistry, Inorganic & Nuclear

Stretching bonds in main group element compounds - Borderlines between biradicals and closed-shell species

Frank Breher

COORDINATION CHEMISTRY REVIEWS (2007)

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Review Chemistry, Multidisciplinary

Glossary of terms used in Photochemistry 3(rd) Edition (IUPAC Recommendations 2006)

S. E. Braslavsky

PURE AND APPLIED CHEMISTRY (2007)

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Study of singlet-triplet transitions in the ozone molecule using the multiconfigurational self-consistent field theory

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HIGH ENERGY CHEMISTRY (2006)

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Ab initio quantum chemistry calculations on the electronic structure of heavier alkyne congeners: Diradical character and reactivity

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2006)

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Lost topological (Berry) phase factor in electronic structure calculations. Example: The ozone molecule

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PHYSICAL REVIEW LETTERS (2006)

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Synthesis of the sterically encumbering terphenyl silyl and alkyl amines HN(R)ArMes2 (R = Me and SiMe3) their lithium derivatives LiN(R)ArMes2 and the tertiary amine Me2NArMes2

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INORGANICA CHIMICA ACTA (2006)

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Article Chemistry, Inorganic & Nuclear

Nature of the chemical bond in polypnictides:: The lone pair aromatic anions P42- and As42-

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INORGANIC CHEMISTRY (2006)

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Review Chemistry, Multidisciplinary

Pulse EPR methods for studying chemical and biological samples containing transition metals

Carlos Calle et al.

HELVETICA CHIMICA ACTA (2006)

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Review Chemistry, Multidisciplinary

Charge-shift bonding - A class of electron-pair bonds that emerges from valence bond theory and is supported by the electron localization function approach

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CHEMISTRY-A EUROPEAN JOURNAL (2005)

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Electronic Structures and Molecular Properties of Chalcogen Nitrates Se2N2 and SeSN2

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JOURNAL OF PHYSICAL CHEMISTRY A (2005)

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Syntheses and reactivity of novel unsaturated cyclic compounds containing phosphorus atoms

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JOURNAL OF ORGANOMETALLIC CHEMISTRY (2005)

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Synthesis and some reactivity studies of germanium, tin and lead analogues of alkynes

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APPLIED ORGANOMETALLIC CHEMISTRY (2005)

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Electronic structures and properties of twisted polyacenes

JE Norton et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2005)

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Second hyperpolarizability (γ) of singlet diradical system:: Dependence of γ on the diradical character

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JOURNAL OF PHYSICAL CHEMISTRY A (2005)

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Stable cyclic (alkyl) (amino) carbenes as rigid or flexible, bulky, electron-rich ligands for transition-metal catalysts: A quaternary carbon atom makes the difference

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Aromaticity of four-membered-ring 6π-electron systems:: N2S2 and Li2C4H4

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2004)

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Article Chemistry, Multidisciplinary

Radical-type reactivity of the 1,3-dibora-2,4-diphosphoniocyclobutane-1,3-diyl

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Synthesis and characterization of Ge2{Sn(X)A#}3 and Ga2{Ge(X)Ar#}3 (Ar# = C6H3-2,6-Mes2), X = (Cl/I):: Rare examples of mixed heavier group 14/14, 13/14 element clusters

AF Richards et al.

ORGANOMETALLICS (2004)

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Article Chemistry, Physical

Electronic structures and spectroscopic properties of 6π-electron ring molecules and ions E2N2 and E42+ (E = S, Se, Te)

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JOURNAL OF PHYSICAL CHEMISTRY A (2004)

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Article Chemistry, Multidisciplinary

Oligoacenes: Theoretical prediction of open-shell singlet diradical ground states

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2004)

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Article Chemistry, Multidisciplinary

Synthesis and characterization of the non-kekule, singlet biradicaloid Ar'Ge(μ-NSiMe3)2GeAr′ (Ar′=2,6-dipp2C6H3, dipp=2,6-i-Pr2C6H3)

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Evidence for the coexistence of two bond-stretch isomers in solution

A Rodriguez et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2004)

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Article Chemistry, Multidisciplinary

The first structural characterisation of a group 2 metal alkylperoxide complex:: Comments on the cleavage of dioxygen by magnesium alkyl complexes

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CHEMISTRY-A EUROPEAN JOURNAL (2003)

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Review Chemistry, Multidisciplinary

Analysis and interpretation of metal-radical coupling in a series of square planar nickel complexes:: Correlated ab initio and density functional investigation of [Ni(LISQ)2] (LISQ=3,5-di-tert-butyl-o-diiminobenzosemiquinonate(1-))

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2003)

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The vibrational spectrum of cyclic ozone

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JOURNAL OF CHEMICAL PHYSICS (2003)

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Utility of neodymium diiodide as a reductant in ketone coupling reactions

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ORGANIC LETTERS (2003)

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Large scale synthesis of dysprosium and neodymium diiodides

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INORGANIC CHEMISTRY (2003)

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Review Chemistry, Multidisciplinary

Physical mechanisms of generation and deactivation of singlet oxygen

C Schweitzer et al.

CHEMICAL REVIEWS (2003)

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Article Chemistry, Physical

How diradicaloid is a stable diradical?

YS Jung et al.

CHEMPHYSCHEM (2003)

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Article Chemistry, Physical

Metastable states of ozone calculated on an accurate potential energy surface

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JOURNAL OF CHEMICAL PHYSICS (2003)

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Review Chemistry, Inorganic & Nuclear

The titanocene complex of bis(trimethylsilyl)acetylene: Synthesis, structure, and chemistry

U Rosenthal et al.

ORGANOMETALLICS (2003)

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Review Chemistry, Multidisciplinary

Persistent and stable radicals of the heavier main group elements and related species

PP Power

CHEMICAL REVIEWS (2003)

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Article Chemistry, Physical

n-electron valence state perturbation theory:: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants

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JOURNAL OF CHEMICAL PHYSICS (2002)

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Article Chemistry, Physical

The asymptotic region of the potential energy surfaces relevant for the O(3P)+O2(X 3Σg-)⇆O3 reaction

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JOURNAL OF CHEMICAL PHYSICS (2002)

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Article Chemistry, Multidisciplinary

Isolable silyl and germyl radicals lacking conjugation with π-bonds:: Synthesis, characterization, and reactivity

A Sekiguchi et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2002)

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Article Chemistry, Inorganic & Nuclear

Theoretical evidence for the singlet diradical character of square planar nickel complexes containing two ο-semiquinonato type ligands

V Bachler et al.

INORGANIC CHEMISTRY (2002)

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Review Chemistry, Physical

The vibrational energies of ozone up to the dissociation threshold:: Dynamics calculations on an accurate potential energy surface

R Siebert et al.

JOURNAL OF CHEMICAL PHYSICS (2002)

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Article Multidisciplinary Sciences

Singlet diradicals: from transition states to crystalline compounds

D Scheschkewitz et al.

SCIENCE (2002)

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Article Chemistry, Multidisciplinary

An isolated cyclo-tetraarsendiide: low temperature synthesis and crystal structure of bis-pentaamminesodium tetraarsendiide-ammonia (1/3) [Na(NH3)(5)](2)As-4 center dot 3NH(3)

N Korber et al.

CHEMICAL COMMUNICATIONS (2002)

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Article Chemistry, Physical

N-electron valence state perturbation theory:: a fast implementation of the strongly contracted variant

C Angeli et al.

CHEMICAL PHYSICS LETTERS (2001)

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Article Chemistry, Physical

Introduction of n-electron valence states for multireference perturbation theory

C Angeli et al.

JOURNAL OF CHEMICAL PHYSICS (2001)

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Review Chemistry, Multidisciplinary

Modern aspects of the Jahn-Teller effect theory and applications to molecular problems

IB Bersuker

CHEMICAL REVIEWS (2001)

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Article Chemistry, Multidisciplinary

Photodissociation of ethylene sulfide at 193 nm: A photofragment translational spectroscopy study with VUV synchrotron radiation and ab initio calculations

F Qi et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2001)

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Review Chemistry, Inorganic & Nuclear

Unusual structures of main group organometallic compounds containing m-terphenyl ligands

JAC Clyburne et al.

COORDINATION CHEMISTRY REVIEWS (2000)

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Article Chemistry, Physical

Ab initio computations of effective exchange integrals for H-H, H-He-H and Mn2O2 complex:: comparison of broken-symmetry approaches

T Soda et al.

CHEMICAL PHYSICS LETTERS (2000)

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