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91.
    
The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B3H4+ analogues.  相似文献   
92.
    
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited‐state redox potentials, PC*/PC.? (up to 1.65 V) and PC.+/PC* (up to ?1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis.  相似文献   
93.
Nimustine hydrochloride [systematic name: 4‐amino‐5‐({[N‐(2‐chloroethyl)‐N‐nitrosocarbamoyl]amino}methyl)‐2‐methylpyrimidin‐1‐ium chloride], C9H14ClN6O2+·Cl, is a prodrug of CENU (chloroethylnitrosourea) and is used as a cytostatic agent in cancer therapy. Its crystal structure was determined from laboratory X‐ray powder diffraction data. The protonation at an N atom of the pyrimidine ring was established by solid‐state NMR spectroscopy.  相似文献   
94.
Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well‐defined 41 helix in which the perylene molecules (see figure) form four “helter‐skelter‐like” overlapping pathways along which excitons and electrons can rapidly migrate.

  相似文献   

95.
The silicon–tin chemical bond has been investigated by a study of the SiSn diatomic molecule and a number of new polyatomic SixSny molecules. These species, formed in the vapor produced from silicon–tin mixtures at high temperature, were experimentally studied by using a Knudsen effusion mass spectrometric technique. The heteronuclear diatomic SiSn, together with the triatomic Si2Sn and SiSn2 and tetratomic Si3Sn, Si2Sn2, and SiSn3 species, were identified in the vapor and studied in the overall temperature range 1474–1944 K. The atomization energy of all the above molecules was determined for the first time (values in kJ mol?1): 233.0±7.8 (SiSn), 625.6±11.6 (Si2Sn), 550.2±10.7 (SiSn2), 1046.1±19.9 (Si3Sn), 955.2±26.8 (Si2Sn2), and 860.2±19.0 (SiSn3). In addition, a computational study of the ground and low‐lying excited electronic states of the newly identified molecules has been made. These electronic‐structure calculations were performed at the DFT‐B3LYP/cc‐pVTZ and CCSD(T)/cc‐pVTZ levels, and allowed the estimation of reliable molecular parameters and hence the thermal functions of the species under study. Computed atomization energies were also derived by taking into account spin–orbit corrections and extrapolation to the complete basis‐set limit. A comparison between experimental and theoretical results is presented. Revised values of (716.5±16) kJ mol?1 (Si3) and (440±20) kJ mol?1 (Sn3) are also proposed for the atomization energies of the Si3 and Sn3 molecules.  相似文献   
96.
97.
The condensation of dialkyl β‐diesters with various aldehydes promoted by TiCl4 has been studied by DFT approaches and experimental methods, including NMR, IR and UV/Vis spectroscopy. Various possible reaction pathways have been investigated and their energy profiles evaluated to find out a plausible mechanism of the reaction. Theoretical results and experimental evidence point to a three‐step mechanism: 1) Ti‐induced formation of the enolate ion; 2) aldol reaction between the enolate ion and the aldehyde, both coordinated to titanium; and 3) intramolecular elimination that leads to a titanyl complex. The presented mechanistic hypothesis allows one to better understand the pivotal role of titanium(IV) in the reaction.  相似文献   
98.
The reaction of [CpRuCl(PPh3)2] (Cp=cyclopentadienyl) and [CpRuCl(dppe)] (dppe=Ph2PCH2CH2PPh2) with bis‐ and tris‐phosphine ligands 1,4‐(Ph2PC≡C)2C6H4 ( 1 ) and 1,3,5‐(Ph2PC≡C)3C6H3 ( 2 ), prepared by Ni‐catalysed cross‐coupling reactions between terminal alkynes and diphenylchlorophosphine, has been investigated. Using metal‐directed self‐assembly methodologies, two linear bimetallic complexes, [{CpRuCl(PPh3)}2(μ‐dppab)] ( 3 ) and [{CpRu(dppe)}2(μ‐dppab)](PF6)2 ( 4 ), and the mononuclear complex [CpRuCl(PPh3)(η1‐dppab)] ( 6 ), which contains a “dangling arm” ligand, were prepared (dppab=1,4‐bis[(diphenylphosphino)ethynyl]benzene). Moreover, by using the triphosphine 1,3,5‐tris[(diphenylphosphino)ethynyl]benzene (tppab), the trimetallic [{CpRuCl(PPh3)}33‐tppab)] ( 5 ) species was synthesised, which is the first example of a chiral‐at‐ruthenium complex containing three different stereogenic centres. Besides these open‐chain complexes, the neutral cyclic species [{CpRuCl(μ‐dppab)}2] ( 7 ) was also obtained under different experimental conditions. The coordination chemistry of such systems towards supramolecular assemblies was tested by reaction of the bimetallic precursor 3 with additional equivalents of ligand 2 . Two rigid macrocycles based on cis coordination of dppab to [CpRu(PPh3)] were obtained, that is, the dinuclear complex [{CpRu(PPh3)(μ‐dppab)}2](PF6)2 ( 8 ) and the tetranuclear square [{CpRu(PPh3)(μ‐dppab)}4](PF6)4 ( 9 ). The solid‐state structures of 7 and 8 have been determined by X‐ray diffraction analysis and show a different arrangement of the two parallel dppab ligands. All compounds were characterised by various methods including ESIMS, electrochemistry and by X‐band ESR spectroscopy in the case of the electrogenerated paramagnetic species.  相似文献   
99.
The Electron Spin Noise Scanning Tunnelling Microscopy (ESN-STM) technique is one of the most promising techniques detecting one single spin, combining the spatial resolution of the STM with the ability of spectral resolution and spin manipulation of Electron Spin Resonance. After its first observation, the effectiveness of this technique has been tested by different groups to study the properties of small aggregates or single organic radical molecules.We report on the ongoing ESN-STM study on nano-aggregates of tris(2,4,6-thrichlorophenyl)methyl radical (TTM) derivatives, whose possibility to be used as wires, switches and memory devices has already been investigated in bulk. After deposition on Au(111), TTM radicals preserved their magnetism. To treat the collected noise data we followed a statistical approach; some peculiar characteristics of this analysis will be addressed.  相似文献   
100.
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