Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Synthesis,Structure, Optical,and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays

Understanding the details of the electronic structure in face‐to‐face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (‐S(CH₂)_nS‐, n=1–4) as models of triple‐ and quadruple‐decker TTF arrays. Single‐crystal X‐ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi‐electron transfers, depending on the length of the ‐S(CH₂)_nS‐ units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630–1850 nm), attributed to a mixed valence (MV) state of the triple‐ and quadruple‐decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent‐dependent redox processes were observed. Moreover, π‐trimers and π‐tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.     

Thermally Tunable Hydrogels Displaying Angle‐Independent Structural Colors

We report the preparation of thermally tunable hydrogels displaying angle‐independent structural colors. The porous structures were formed with short‐range order using colloidal amorphous array templates and a small amount of carbon black (CB). The resultant porous hydrogels prepared using colloidal amorphous arrays without CB appeared white, whereas the hydrogels with CB revealed bright structural colors. The brightly colored hydrogels rapidly changed hues in a reversible manner, and the hues varied widely depending on the water temperature. Moreover, the structural colors were angle‐independent under diffusive lighting because of the isotropic nanostructure generated from the colloidal amorphous arrays.     

Single Crystalline,Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks

Porous frameworks composed of non-stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives ( CP-Hp and CP-Py , respectively) yields non-stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP-Hp and CP-Py in the framework was determined by single crystalline X-ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.     

A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State

Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.     

Radiative melting of a horizontal clear ice layer

In this paper the horizontal layer of clear ice sticking to the substrate is melted by comparatively short wave radiation similar to solar radiation for the purpose of removing ice from the surface of the material subject to atmospheric icing. The radiating source used for melting is 300 wattages halogen lamps whose color temperature is 3200K at 100 voltages. From the present investigation, a typical phenomenon of backmelting is observed clearly and it can be found that the predicted results including the melting rate of upper and lower layers which are melted by radiant energy impinged on or penetrated the ice layer are in good agreement with the experimental results.

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Aufschmelzen einer waagerechten Klareisschicht durch Strahlung

Zusammenfassung Eine waagerechte Klareisschicht, die auf einer Unterlage aufgefroren war, wurde durch kurzwellige Strahlung, Ähnlich der Sonnenstrahlung, zum Schmelzen gebracht, um die Entfernung von Eis nach atmosphÄrischer Vereisung zu untersuchen. Die Strahlungsquelle war eine 300 Watt-Halogenlampe mit einer Farbtemperatur von 3200 Kelvin bei 100 Volt. Als typische Erscheinung wurde ein Rückseiten-Schmelzen gefunden, im übrigen sind die vorausberechneten Schmelzraten an der Ober- und der Unterseite durch aufgenommene oder durchgelassene Strahlungsenergie in guter übereinstimmung mit den Messungen.

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Nomenclature a_v monochromatic absorption coefficient - A transmission (= q _r ⁺ {h_i}/q_ro) - c_p specific heat - E_bv monochromatic emissive power - h_D mass transfer coefficient - h_i initial thickness of ice layer - h_m thickness of substrate - L_i latent heat of melting - L_w latent heat of evaporation or condensation - heat flux absorbed at surface of substrate - q_r0 radiant heat flux impinged onto ice or free surface - q _r ⁺ {y} forward radiant heat flux - q _r ^– {y} backward radiant heat flux - S₁ thickness of upper melt layer - S₂ thickness of lower melt layer - S'₂ distance from free surface to bottom surface of ice layer - t time - T temperature - T₁ temperature of air-water or air-ice interface - T₂ temperature of substrate surface - T₃ temperature of back side surface of substrate - T_b temperature of radiating source - T_i temperature in ice layer - T_w1 temperature in upper melt layer - T_w2 temperature in lower melt layer - T environmental temperature - W_w saturated vapor concentration at free surface - W_t8 vapor concentration at environment - y distance from free or ice surface - y grid size of water or ice - y_m grid size of substrate Greek symbols heat transfer coefficient - spectral absorptivity - _t total absorptivity - _i thermal diffusivity of ice - _m thermal diffusivity of substrate - _w thermal diffusivity of water - _i thermal conductivity of ice - _m thermal conductivity of substrate - _w thermal conductivity of water - wavelength - _av densitiy of air-vapor mixture - _i density of ice - Stefan-Boltzman constant     

Radiative melting of ice layer adhering to a vertical surface

This paper is concerned with melting of a vertical ice layer adhering to the substrate by using radiating heat source of halogen lamps having a large fraction of short wave beam or nichrome heater having a comparatively large fraction of long wave one. From the present experimental results, it can be seen that the heating of short wave radiation produces a peculiar melting behavior of strongly rough melting-surface due to the internal melting at the grain boundary of ice-surface. On the other hand, for the case of long wave radiation the melting-surface becomes very smooth. The melting rate of clear ice layer by short wave radiation obtained from halogen lamps is smaller than that of cloudy ice layer due to the good penetration of short wave fraction through the clear ice layer. Moreover, the raising of temperature of ice-substrate interface could offer a feasibility of removing ice layer from the structure subject to atmospheric icing. Concludingly, it is clarified that the melting rate of ice layer could be predicted numerically by using the band model of extinction coefficient or absorption coefficient presented in this study.

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Schmelzen einer Eisschicht an einer senkrechten Wand durch Strahlung

Zusammenfassung Diese Arbeit behandelt das Schmelzen einer senkrechten Eisschicht auf einer Unterlage mit Hilfe von Halogen-Lampen mit einem hohen Anteil an kurzen Wellen und Nichromheizern mit einem hohen Anteil an langen Wellen. Aus diesen Versuchen läßt sich ableiten, daß die Heizung durch kurzwellige Strahlung ein eigentümliches Schmelzverhalten mit sehr rauher Oberfläche hervorruft, verursacht durch Schmelzen an den Korngrenzen der Eisoberfläche. Bei langwelliger Heizung wird die Oberfläche sehr glatt. Die Abschmelzrate einer Klareisschicht bei kurzwelliger Heizung durch Halogen-Lampen ist geringer als die einer Opaleisschicht wegen des besseren Eindringens der kurzen Wellen in das klare Eis. Der Temperaturanstieg an der Grenze Eis — Unterlage bietet die Möglichkeit der Enteisung von Bauteilen, die der atmosphärischen Vereisung ausgesetzt sind. Es folgt, daß die Abschmelzrate einer Eisschicht, numerisch vorausberechnet werden kann, indem man das Bandmodell des Extinktions- und des Absorptionskoeffizienten dieser Arbeit verwendet.

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Nomenclature A transmission, defined in equation (4) - a monochromatic absorption coefficient of clear ice - C constant - E_b monochromatic emissive power - h_i thickness of ice layer - h_in initial thickness of ice layer - h_m thickness of substrate - k₀ extinction coefficient for h₀ 0 - k_s modified extinction coefficient - k monochromatic extinction coefficient - L_i latent heat of melting - n index number, defined in equation (2) - heat flux absorbed at surface of substrate - q_r0 radiant heat flux impinged onto ices-urface - q_ri{y} radiant heat flux in ice layer - S distance from initial ice-surface to transient melting-surface - T_b temperature of radiating heat source - T_i temperature in ice layer - T_m temperature in substrate - T environmental temperature - T₁ temperature of surface of ice layer - T₂ temperature of substrate-surface - T₃ temperature of back side surface of substrate - t time - y distance from initial ice-surface - Z ratio of backward radiative heat flux to forward one for cloudy ice Greek Symbols heat transfer coefficient - _i thermal diffusivity of ice - _m thermal diffusivity of substrate - _i thermal conductivity of ice - _m thermal conductivity of substrate - wavelength - _c critical wavelength - _i density of ice - Stefan-Boltzmann constant     

Single-phase heat transfer characteristics of concentric-tube thermosyphon

An experimental study has been conducted to evaluate the influence of the presence of inner tube and the Rayleigh number on free convective heat transfer in an open thermosyphon. Water and fluorocarbon R-11 refrigerant as the working fluids were utilized. Heat transfer results using the concentric geometry were given for modified Rayleigh number from 3.6×10² to 4.1 × 10⁷ which encompasses the regions of similarity, impeded and boundary layer flow conditions. It was found that the presence of the inner tube markedly increases the overall heat transfer coefficient of open thermosyphon by a factor as large as 2 to 10 in the turbulent impeded and boundary layer regimes.

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Wärmeübergang in einem Thermosyphon aus konzentrischem Rohr bei einphasiger Strömung

Zusammenfassung Es wurde experimentell untersucht, wie der Einbau eines Innenrohres und wie die Rayleigh-Zahl auf die freie Konvektion in einem offenen Thermosyphon, gefüllt mit Wasser oder dem Kältemittel R 11, einwirkt. Der untersuchte Bereich bei konzentrischer Geometrie lag bei modifizierten Rayleigh-Zahlen von 3,6 · 10² bis 4,1 · 10⁷ und umfaßte damit die Regionen der Grenzschichtströmung. Es ergab sich, daß der Einbau eines Innenrohres den Gesamtwärmeübergang eines offenen Thermosyphons im Bereich der behinderten turbulenten Strömungen und Grenzschichtströmungen um den Faktor 2 bis 10 steigert.

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Nomenclature a inner radius of heated tube, D/2 - A_in sectional space area of inner tube, d _i ² /4 - A_an sectional space area of annulus, (D^2-d ₀ ² )/4 - C_p specific heat - d_i inner diameter of inner tube - d₀ outer diameter of inner tube - D inner diameter of heated tube - g gravitational acceleration - L tube length of thermosyphon - Nu_a Nusselt number based on inner radius of heated tube - Nu_r Nusselt number based on equivalent heattransfer radius - Nu_x Nusselt number, defined in equation (1) - Pr Prandtl number, defined in equation (3) - q heat flux from heated tube - r equivalent heat-transfer radius, defined in equation (4) - Ra_a modified Rayleigh number based on inner radius of heated tube - Ra_r modified Rayleigh number based on equivalent heat-transfer radius - Ra_x modified Rayleigh number, defined in equation (2) - T_e temperature of entrance-fluid - T_w temperature of heated surface - T temperature difference between heated wall and entrance-fluid, T_w-T_e Greek Symbols coefficient of volumetric expansion - thermal diffusivity - thermal conductivity - viscosity - kinematic viscosity