Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

Relaxation Processes and Exciton-Phonon Interactions in Nanocomposites Based on CdSe/ZnS Semiconductor Quantum Dots and Porphyrin Molecules

Russian Physics Journal - Using spectral-kinetic data obtained for nanoassemblies based on CdSe/ZnS semiconductor quantum dots and tetrapyridylporphyrin molecules in methylcyclohexane-toluene...     

The fluorine-NHC gauche effect: a structural and computational study

Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural feature of these species is a flanking fluoroethyl group, which is either freely rotating or embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational preference in all cases with the fluorine adopting a syn clinal arrangement (?_[NCCF]～60°) with respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory analysis was employed to quantify these effects and evaluate the influence of electronic modulation of the carbenic carbon [(CN⁺); neutral carbene (C:); metal-bound carbene (CM)], on the relative gauche/anti preference, thus highlighting the potential of this conformational phenomenon as a useful molecular design strategy for controlling the topology of organometallic complexes.     

Ultrasound velocimetry of ferrofluid spin-up flow measurements using a spherical coil assembly to impose a uniform rotating magnetic field

Ferrofluid spin-up flow is studied within a sphere subjected to a uniform rotating magnetic field from two surrounding spherical coils carrying sinusoidally varying currents at right angles and 90° phase difference. Ultrasound velocimetry measurements in a full sphere of ferrofluid shows no measureable flow. There is significant bulk flow in a partially filled sphere (1-14 mm/s) of ferrofluid or a finite height cylinder of ferrofluid with no cover (1-4 mm/s) placed in the spherical coil apparatus. The flow is due to free surface effects and the non-uniform magnetic field associated with the shape demagnetizing effects. Flow is also observed in the fully filled ferrofluid sphere (1-20 mm/s) when the field is made non-uniform by adding a permanent magnet or a DC or AC excited small solenoidal coil. This confirms that a non-uniform magnetic field or a non-uniform distribution of magnetization due to a non-uniform magnetic field are causes of spin-up flow in ferrofluids with no free surface, while tangential magnetic surface stress contributes to flow in the presence of a free surface.Recent work has fitted velocity flow measurements of ferrofluid filled finite height cylinders with no free surface, subjected to uniform rotating magnetic fields, neglecting the container shape effects which cause non-uniform demagnetizing fields, and resulting in much larger non-physical effective values of spin viscosity η′∼10⁻⁸−10⁻¹² N s than those obtained from theoretical spin diffusion analysis where η′≤10⁻¹⁸ N s. COMSOL Multiphysics finite element computer simulations of spherical geometry in a uniform rotating magnetic field using non-physically large experimental fit values of spin viscosity η′∼10⁻⁸−10⁻¹² N s with a zero spin-velocity boundary condition at the outer wall predicts measureable flow, while simulations setting spin viscosity to zero (η′=0) results in negligible flow, in agreement with the ultrasound velocimetry measurements. COMSOL simulations also confirm that a non-uniform rotating magnetic field or a uniform rotating magnetic field with a non-uniform distribution of magnetization due to an external magnet or a current carrying coil can drive a measureable flow in an infinitely long ferrofluid cylinder with zero spin viscosity (η′=0).     

Negative electrorheological responses of micro-polar fluids in the finite spin viscosity small spin velocity limit. I. Couette flow geometries

Negative electrorheological responses induced by micro-particle electrorotation in two-dimensional Couette flow geometries are analyzed by a set of continuum modeling field equations originating from anti-symmetric/couple stress theories in the finite spin viscosity small spin velocity (FSV) limit. Analytical solutions are obtained for the first time to express the spin velocity, linear velocity, and effective viscosity in terms of the electric field strength, driving shear rate, boundary condition selection parameter, and spin viscosity. Good agreement is achieved between the FSV theoretical predictions presented herein and the experimental measurements reported in recent literature for the effective viscosity for low driving shear rates.     

Synthesis and characterization of novel amino cellulose esters

The homogeneous conversion of cellulose dissolved in N-methyl-2-pyrrolidone/LiCl and 1-N-butyl-3-methylimidazolium chloride with N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, and N-methyl-2-piperidone in the presence of p-toluenesulphonic acid chloride was studied. Depending on the reaction conditions, novel cellulose esters with degree of substitution (DS) values ranging from 0.12 to 1.17 could be prepared. The structure of the amino group containing cellulose esters was elucidated by elemental analysis, FTIR- and NMR spectroscopy. NMR spectroscopy revealed an almost complete esterification of position 6 of the anhydroglucose unit at DS of 1. The conversion can be conducted between room temperature and 40 °C, while side-reactions became predominant at 60 °C. Starting with DS of 0.24, the samples were soluble both in water and dimethyl sulphoxide. The derivatives described are capable of forming polyelectrolyte complexes. The samples were stable at room temperature in aqueous solution at pH 2 and 7. Lower viscosities were found for samples with higher DS in aqueous solution at comparable molar mass.