`Picket‐fence' porphyrin compounds are used in the investigation of interactions of hemes with dioxygen, carbon monoxide, nitric monoxide and imidazole ligands. (Cryptand‐222)potassium chlorido[meso‐tetra(α,α,α,α‐o‐pivalamidophenyl)porphyrinato]manganese tetrahydrofuran monosolvate (cryptand‐222 is 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane), [K(C18H36N2O6)][Mn(C64H64N8O4)Cl]·C4H8O or [K(222)][Mn(TpivPP)Cl]·THF [systematic name for TpivPP: 5,10,15,20‐tetrakis(2‐tert‐butanamidophenyl)porphyrin], is a five‐coordinate high‐spin manganese(II) picket‐fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand‐222 molecule; the average K—O and K—N distances are 2.83 (4) and 2.995 (13) Å, respectively. All four protecting tert‐butyl pickets of the porphyrin are ordered. The porphyrin plane is nearly planar, as indicated by the atomic displacements and the dihedral angles between the mean planes of the pyrrole rings and the 24‐atom mean plane. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Mn—Cl bond is tilted slightly off the normal to the porphyrin plane by 3.68 (2)°. The out‐of‐plane displacement of the metal centre relative to the 24‐atom mean plane (Δ24) is 0.7013 (4) Å, indicating a noticeable porphyrin core doming. 相似文献
A new non‐innocent ligand redox system, N,N′‐bis(4‐dimethylaminophenyl) substituted acetamidinato/acetamidinyl, has been designed and described by example of structurally and spectroscopically characterized ruthenium complexes. The hitherto unreported ligand is responsible for rather intense and narrow absorptions in the near‐infrared region of the one‐ and two‐electron oxidized forms. The spectroscopic, computational, and first structural characterization of an amidinyl radical complex adds to the list of established N‐based radical ligands. 相似文献
Low‐bandgap near‐infrared polymers are usually synthesized using the common donor–acceptor (D–A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D–A1–D–A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single‐component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D–A1–D–A2 polymers as the electron donor mixed with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short‐circuit current densities (J sc) of around 11 mA cm−2, high fill factors up to 0.70, and high open‐circuit voltages (V ocs) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll‐to‐roll large‐scale manufacturing processes.
This paper presents a study of the fundamental mechanics of droplet and gas motion in sprays. Only vertical sprays are considered and our theoretical analysis identifies two main flow zones, corresponding to where the droplet velocity is much greater than or of the same order as the induced air velocity. Analytical asymptotic results for the induced air velocity for small and large downstream distances confirmed a full numerical calculation and also agreed with experimental results. The second half of the paper deals with some of the most important aspects of spray jets in a cross flow. We find that the ratio of the cross-wind speed to the induced air jet speedU0/Vjis a crucial factor for specifying the dynamical behaviour. We present results for an axi-symmetric spray in uniform cross flow for bothweak andstrong cross-winds. 相似文献