Three trithiadiazepines and a trithiatriazepine

The structures of 6‐nitro‐1,3λ⁴δ²,5,2,4‐trithiadiazepine [C₂HN₃O₂S₃, ( 1 )], 6,7‐dinitro‐1,3λ⁴δ²,5,2,4‐trithiadiazepine [C₂N₄O₄S₃, ( 2 )], 1,3λ⁴δ²,5,2,4‐trithiadiazepine‐6,7‐dicarbonitrile [C₄N₄S₃, ( 3 )] and 7‐acetyl‐1,3λ⁴δ²,5,2,4,6‐trithiatriazepine [C₃H₃N₃OS₃, ( 4 )] presented here include the most precise determinations of these seven‐membered 10 π‐electron aromatic ring systems published to date. Both ( 2 ) and ( 3 ) are sited around crystallographic twofold axes with half a molecule per asymmetric unit. Comparison with other published derivatives of these rings reveals the effect of substituents on bonding, conformations and intermolecular interactions, including π‐stacking. The deformation density analysis of ( 2 ) is consistent with the expected bonding electron density from other theoretical and experimental studies.     

Hydrogen bonding in 4‐nitrobenzene‐1,2‐diamine and two hydrohalide salts

The structures of 4‐nitrobenzene‐1,2‐diamine [C₆H₇N₃O₂, (I)], 2‐amino‐5‐nitroanilinium chloride [C₆H₈N₃O₂⁺·Cl⁻, (II)] and 2‐amino‐5‐nitroanilinium bromide monohydrate [C₆H₈N₃O₂⁺·Br⁻·H₂O, (III)] are reported and their hydrogen‐bonded structures described. The amine group para to the nitro group in (I) adopts an approximately planar geometry, whereas the meta amine group is decidedly pyramidal. In the hydrogen halide salts (II) and (III), the amine group meta to the nitro group is protonated. Compound (I) displays a pleated‐sheet hydrogen‐bonded two‐dimensional structure with R₂²(14) and R₄⁴(20) rings. The sheets are joined by additional hydrogen bonds, resulting in a three‐dimensional extended structure. Hydrohalide salt (II) has two formula units in the asymmetric unit that are related by a pseudo‐inversion center. The dominant hydrogen‐bonding interactions involve the chloride ion and result in R₄²(8) rings linked to form a ladder‐chain structure. The chains are joined by N—H...Cl and N—H...O hydrogen bonds to form sheets parallel to (010). In hydrated hydrohalide salt (III), bromide ions are hydrogen bonded to amine and ammonium groups to form R₄²(8) rings. The water behaves as a double donor/single acceptor and, along with the bromide anions, forms hydrogen bonds involving the nitro, amine, and ammonium groups. The result is sheets parallel to (001) composed of alternating R₅⁵(15) and R₆⁴(24) rings. Ammonium N—H...Br interactions join the sheets to form a three‐dimensional extended structure. Energy‐minimized structures obtained using DFT and MP2 calculations are consistent with the solid‐state structures. Consistent with (II) and (III), calculations show that protonation of the amine group meta to the nitro group results in a structure that is about 1.5 kJ mol⁻¹ more stable than that obtained by protonation of the para‐amine group. DFT calculations on single molecules and hydrogen‐bonded pairs of molecules based on structural results obtained for (I) and for 3‐nitrobenzene‐1,2‐diamine, (IV) [Betz & Gerber (2011). Acta Cryst. E 67 , o1359] were used to estimate the strength of the N—H...O(nitro) interactions for three observed motifs. The hydrogen‐bonding interaction between the pairs of molecules examined was found to correspond to 20–30 kJ mol⁻¹.     

Synthesis and Conformation of 3,6‐Connected Cyclohexadiene Chains

3,6‐Connected cyclohexadienes as precursors for polyphenylenes are synthesized and characterized by mass spectrometry and NMR spectroscopy. Pure fractions of trimers, hexamers, and nonamers are collected after separation of the product mixture by recycling GPC. The anticipated formation of rigid linear structures, due to the trans‐configuration of the monomeric units, is supported by density functional theory and experimentally confirmed by dynamic light scattering from dilute solution at low scattering angles. The obtained translational diffusion coefficients are represented by rigid rod‐like or prolate ellipsoid‐like molecular shapes. The measurements of diffusion coefficients reveal a length‐dependent ratio of 1:2:3 between the three oligomers, which directly correlates to the expected length extension from trimer to nonamer.

     

Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis,Crystallographic Characterization and Reactivity of a Phosphinine-B(C6F5)3 Lewis Pair

A phosphinine-borane adduct of a Me₃Si-functionalized phosphinine and the Lewis acid B(C₆F₅)₃ has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B₂H₆ with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct ( 6 -B(C₆F₅)₃) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me₃Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts.     

铀酰与羧酸和肟基类配体相互作用的理论研究

深入了解各种功能基团与铀酰离子的络合行为有助于设计和开发高效海水提铀吸附剂. 本工作通过密度泛函理论(DFT)方法系统地研究了两种典型铀酰络合配体吡啶-2,6-二羧酸(H₂DPA)和戊二酰偕亚胺二肟(H₂A)与铀酰离子及碳酸根离子形成的配合物的结构、成键性质以及热力学稳定性. 研究结果表明, 所有配合物中, 配体与铀酰离子之间具有不同强度的共价相互作用. 由于H₂A配位时发生了质子重排, 而且配体的解离能较高, 使其更难与[UO₂(CO₃)₃]^4-发生取代反应, 因此H₂DPA配体是海水提铀中一种潜在的有效配体. 本工作的相关研究结果为海水提铀中高效吸附基团的设计和开发提供了理论线索.     

纳米孔缺陷导致单层黑磷电荷局域极大抑制非辐射电子-空穴复合的时域模拟

通常认为缺陷加速黑磷的非辐射电子-空穴复合,阻碍器件性能的持续提高。实验打破了这一认识。采用含时密度泛函理论结合非绝热分子动力学,我们发现P-P伸缩振动驱动非辐射电子-空穴复合,使纳米孔修饰的单层黑磷的激发态寿命比完美体系延长了约5.5倍。这主要归因于三个因素。一,纳米孔结构不但没有在禁带中引入深能级缺陷,而且由于价带顶下移使带隙增加了0.22 eV。二,除了带隙增加,纳米孔减小了电子和空穴波函数重叠,并抑制了原子核热运动,从而使非绝热耦合降低至完美体系的约1/2。三,退相干时间比完美体系延长了1.5倍。前两个因素战胜了第三个因素,使纳米孔结构激发态寿命延长至2.74 ns,而其在完美体系中约为480 ps。我们的研究表明可以制造合理数量和形貌的缺陷,如纳米孔,降低黑磷非辐射电子-空穴复合,提高光电器件效率。这一研究对于理解和调控黑磷和其它二维材料的激发态性质有重要意义。     

Rational Tuning of the Reactivity of Three-Membered Heterocycle Ring Openings via SN2 Reactions

The development of small-molecule covalent inhibitors and probes continuously pushes the rapidly evolving field of chemical biology forward. A key element in these molecular tool compounds is the “electrophilic trap” that allows a covalent linkage with the target enzyme. The reactivity of this entity needs to be well balanced to effectively trap the desired enzyme, while not being attacked by off-target nucleophiles. Here we investigate the intrinsic reactivity of substrates containing a class of widely used electrophilic traps, the three-membered heterocycles with a nitrogen (aziridine), phosphorus (phosphirane), oxygen (epoxide) or sulfur atom (thiirane) as heteroatom. Using quantum chemical approaches, we studied the conformational flexibility and nucleophilic ring opening of a series of model substrates, in which these electrophilic traps are mounted on a cyclohexene scaffold (C₆H₁₀Y with Y=NH, PH, O, S). It was revealed that the activation energy of the ring opening does not necessarily follow the trend that is expected from C−Y leaving-group bond strength, but steeply decreases from Y=NH, to PH, to O, to S. We illustrate that the HOMO_Nu–LUMO_Substrate interaction is an all-important factor for the observed reactivity. In addition, we show that the activation energy of aziridines and phosphiranes can be tuned far below that of the corresponding epoxides and thiiranes by the addition of proper electron-withdrawing ring substituents. Our results provide mechanistic insights to rationally tune the reactivity of this class of popular electrophilic traps and can guide the experimental design of covalent inhibitors and probes for enzymatic activity.     

Phenylene-Bridged Perylene Monoimides as Acceptors for Organic Solar Cells: A Study on the Structure–Property Relationship

A series of non-fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki-coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X-ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB-T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure–property relationships of perylene-linker-perylene compounds.