Popculture in postcolonial literature Motifs of popular culture in Arundhati Roy’s The God of Small Things and Eden Robinson’s Monkey Beach

The reaction of LGa (L = Dipp­(4-(Dipp-imino)­pent-2-en-2-yl)­amide; Dipp: 2,6-diisopropylphenyl) and white phosphorus was revisited. A plethora of unprecedented polyphosphanes in addition to the known monoinserted product LGaP₄ (<b>1</b>) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)₂P₆ (<b>3</b>) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, Ph₂ECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes

Helical Nanographenes Containing an Azulene Unit : Synthesis, Crystal Structures, and Properties

Three unprecedented helical nanographenes (1, 2, and 3) containing an azulene unit are synthesized. The resultant helical structures are unambiguously confirmed by X-ray crystallographic analysis. The embedded azulene unit in 2 possesses a record-high twisting degree (16.1°) as a result of the contiguous steric repulsion at the helical inner rim. Structural analysis in combination with theoretical calculations reveals that these helical nanographenes manifest a global aromatic structure, while the inner azulene unit exhibits weak antiaromatic character. Furthermore, UV/Vis-spectral measurements reveal that superhelicenes 2 and 3 possess narrow energy gaps (2: 1.88 eV; 3: 2.03 eV), as corroborated by cyclic voltammetry and supported by density functional theory (DFT) calculations. The stable oxidized and reduced states of 2 and 3 are characterized by in-situ EPR/Vis–NIR spectroelectrochemistry. Our study provides a novel synthetic strategy for helical nanographenes containing azulene units as well as their associated structures and physical properties. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

On-water surface synthesis of charged two-dimensional polymer single crystals via the irreversible Katritzky reaction

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) are classes of structurally defined crystalline polymeric materials with exotic physical and chemical properties. Yet, synthesizing 2DP and 2D COF single crystals via irreversible reactions remains challenging. Here we report the synthesis of charged 2DP (C2DP) single crystals through an irreversible Katritzky reaction, under pH control, on a water surface. The periodically ordered 2DPs comprise aromatic pyridinium cations and counter BF4− anions. The C2DP crystals, which are composed of linked porphyrin and pyrylium monomers (C2DP-Por), have a tunable thickness of 2–30 nm and a lateral domain size up to 120 μm2. Single crystals with a square lattice (a = b = 30.5 Å) are resolved by imaging and diffraction methods with near-atomic precision. Furthermore, the integration of C2DP-Por crystals in an osmotic power generator device shows an excellent chloride ion selectivity with a coefficient value reaching ~0.9 and an output power density of 4 W m−2, superior to those of graphene and boron nitride

Recent highlights in mixed-coordinate oligophosphorus chemistry

This review aims to highlight and comprehensively summarize recent developments in the field of mixed-coordinate phosphorus chemistry. Particular attention is focused on the synthetic approaches to compounds containing at least two directly bonded phosphorus atoms in different coordination environments and their unexpected properties that are derived from spectroscopic and crystallographic data. Novel substance classes are discussed in order to supplement previous reviews about mixed-coordinate phosphorus compounds

Iron-Gallium and Cobalt-Gallium Tetraphosphido Complexes

The synthesis and characterization of two heterobimetallic complexes [K([18]crown-6){(eta(4)-C14H10)Fe(mu-eta(4):eta(2)-P-4)Ga(nacnac)}] (1) (C14H10 = anthracene) and [K(dme)(2){(eta(4)-C14H10)Co(mu-eta(4):eta(2)-P-4)Ga(nacnac)}] (2) with strongly reduced P-4 units is reported. Compounds 1 and 2 are prepared by reaction of the gallium(III) complex [(nacnac)Ga(eta(2)-P-4)] (nacnac = CH[CMeN(2,6-iPr(2)C(6)H(3))](2)) with bis(anthracene)ferrate(1-) and -cobaltate(1-) salts. The molecular structures of 1 and 2 were determined by X-ray crystallography and feature a P-4 chain which binds to the transition metal atom via all four P atoms and to the gallium atom via the terminal P atoms. Multinuclear NMR studies on 2 suggest that the molecular structure is preserved in solution

Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus

The reaction of LGa (L = Dipp­(4-(Dipp-imino)­pent-2-en-2-yl)­amide; Dipp: 2,6-diisopropylphenyl) and white phosphorus was revisited. A plethora of unprecedented polyphosphanes in addition to the known monoinserted product LGaP₄ (<b>1</b>) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)₂P₆ (<b>3</b>) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, Ph₂ECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes

Nitrogen–Phosphorus(III)–Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes

The synthesis of inorganic N–P­(III)-Ch-based macrocycles [−PhP–NMe–PPh–Ch−]₂ (<b>8</b>_<b>Ch</b>; Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na₂Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP–NMe–PClPh (<b>9</b>). Treatment with elemental sulfur (S₈) or gray selenium (Se_gray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (<b>10</b>_<b>S</b>) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (<b>10</b>_<b>Se</b>), respectively. Macrocycles <b>8</b>_<b>Ch</b> are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis

Nitrogen–Phosphorus(III)–Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes

The synthesis of inorganic N–P­(III)-Ch-based macrocycles [−PhP–NMe–PPh–Ch−]₂ (<b>8</b>_<b>Ch</b>; Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na₂Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP–NMe–PClPh (<b>9</b>). Treatment with elemental sulfur (S₈) or gray selenium (Se_gray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (<b>10</b>_<b>S</b>) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (<b>10</b>_<b>Se</b>), respectively. Macrocycles <b>8</b>_<b>Ch</b> are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis