Diversified Excited-State Relaxation Pathways of Donor–Linker–Acceptor Dyads Controlled by a Bent-to-Planar Motion of the Donor

Herein, we introduce the cyclic 8π-electron (C8π) molecule N,N′-diaryl-dihydrodibenzo[a,c]phenazine ( DPAC ) as a dual-functional donor to establish a series of new donor–linker–acceptor (D–L–A) dyads DLA1 – DLA5 . The excited-state bent-to-planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1 – A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited-state electron transfer vs. energy transfer can be finely harnessed, which is verified via steady-state spectroscopy and time-resolved emission measurements. This comprehensive approach demonstrates, for the first time, the manifold of excited-state properties governed by bifunctional donor-based D–L–A dyads, including bent-to-planar, photoinduced electron transfer (PET) from excited donor to acceptor (oxidative-PET), fluorescence resonance energy transfer (FRET), bent-to-planar followed by electron transfer (PFET), and PET from donor to excited acceptor (reductive-PET).     

Donor–Acceptor Mechanism of Complex Formation

The gas-phase van der Waals complexes formed in the course of donor–acceptor interaction are shown to become coordination compounds only in the crystalline state. With close lengths of the covalent-ionic and coordination bonds, their energies differ by 100 kJ. This energy difference is due to the work spent to overcome van der Waals forces during the formation of complex ions from interacting molecules.     

Synthesis of OMS Materials and Investigation of Their Acceptor–Donor Characteristics

Three ordered mesoporous siliceous (OMS) materials known as MCM41s—unmodified MCM-41C16 (“C16”), and two MCM41s with different surface functionalities: MCM-41C16-SH (“C16-SH”) and MCM-41C16-NH₂ (“C16-NH₂”)—were synthesized and studied by inverse gas chromatography in order to determine their acceptor–donor properties. The specific retention volumes of nonpolar and polar probes that were chromatographed on these ordered mesoporous silica adsorbents were evaluated under infinite dilution conditions. Two methods were employed to calculate the standard free energy of adsorption, ΔG _ads, of each chromatographed probe on the basis its specific retention volume. These ΔG _ads values were then employed to estimate the van der Waals contribution and the specific contribution of the free surface energy for each MCM41. DN values (donor numbers, based on the Gutmann scale) and AN* values (acceptor numbers, based on the Riddle–Fowkes scale) were employed to determine the values of parameters that characterize the ability of the MCM41s to act as electron acceptors (parameter: K _A) and donors (parameter: K _D). Considering the different compositions of the probes, each of which has different acceptor–donor properties, a new chromatographic test to supplement the Grob test is suggested.     

Excited Donor–Acceptor Complexes in the Polymerization of Vinyl Monomers

Butyl methacrylate was found to affect the composition of radical intermediates formed in the photoreduction of benzophenone with triethylamine. In the presence of the monomer, the yield of free radicals decreased and the yield of complexes of the geminate radical pair increased. This was explained by the formation of excited ternary complexes resulted from the interaction of the excited triplet state of benzophenone with the ground-state complex of butyl methacrylate and triethylamine. The substituent effect in benzophenone on the stability of the radical complex was studied. The reaction rate constant for the decay of the radical complex was correlated with the Hammett ⁰ _c constant that determines the mesomeric effect of the substituent.     

Ring-Opening 1,3-Aminochalcogenation of Donor–Acceptor Cyclopropanes: A Three-Component Approach

A 1,3-aminothiolation was realized by reacting 2-substituted cyclopropane 1,1-dicarboxylates with sulfonamides and N-(arylthio)succinimides. Under Sn(OTf)₂ catalysis the transformation proceeded smoothly to the corresponding ring-opened products bearing the sulfonamide in the 1-position next to the donor and the arylthio residue in the 3-position next to the acceptor. The procedure was extended to the corresponding selenium analogues by employing N-(phenylseleno)succinimides as an electrophilic selenium source.     

Acceleration of the Recombination of Photoexcited Donor—Acceptor Complexes with a High-Frequency Vibrational Mode

The recombination dynamics of ion pairs formed by the photoexcitation of donor—acceptor complexes in a polar solvent was investigated using the stochastic approach. The reorganization of high-frequency intramolecular vibrational modes plays an important role in these reactions. It was shown for the perylene—tetracyanoethylene complex in acetonitrile solution that the overwhelming majority of ion pairs recombined at the hot stage, during solvent polarization relaxation.     

Geometrical Changes and Their Energies in the Formation of Donor–Acceptor Complexes

We have mapped the energy demands of the geometrical changes in donor–acceptor complexes BH₃NH₃ and AlCl₃NH₃ and in the course of their formation from their monomers. We have varied the individual geometrical parameters systematically and performed ab initio quantum chemical calculations for these structures. We investigated the energy requirements to change bond lengths and bond angles in both the monomers and complexes and the angles of torsion in the complexes. The changes of bond lengths require more energy in the monomers than in the complexes. The energies to change the acceptor bond angles in the monomers are markedly higher than in the complexes. The changes in the geometrical parameters during the complexation process are more moderate in donors than in acceptors, in agreement with prior experimental observations. The geometry versus energy variations related to the process of complexation are in agreement with the notion of relative rigidity of the donor parts and the more compliant nature of the acceptor parts as well as with the notion of competing effects in the structures of the complexes.     

Synthesis and Photovoltaic Properties of Donor–Acceptor Oligothiophene Derivatives Possessing Mesogenic Properties

For the purpose of developing novel photovoltaic materials and organic photovoltaic devices with good performance characteristics, 5-cyano-2,2′:5′,2″-terthiophene (3T-CN) and 5-cyano-2,2′:5′,2″:5″,2″′-tetrathiophene (4T-CN) were synthesized. The 3T-CN and 4T-CN were donor–acceptor oligothiophene derivatives possessing mesogenic properties. The photovoltaic properties of 3T-CN and 4T-CN were studied. The rigid and flexible photovoltaic devices were fabricated using 3T-CN, 4T-CN, and 3,4,9,10-perylenetertracarboxylic dianhydride (PTCDA). The results showed that the -CN group played an important role in increasing short circuit current density (I _sc) and power conversion efficiency (PCE). Both rigid device glass-ITO/4T-CN/PTCDA/Al and flexible device PET-ITO (indium tin oxides coated with polyethylene terephthalate)/4T-CN/PTCDA/Al had greater I _sc and PCE compared with rigid device glass-ITO/4T/PTCDA/Al. It was possible that the -CN group, with strong electron-withdrawing character, and mesogenic properties of 4T-CN enhanced the efficiency by promoting forward interfacial electron transfer.      

Synthesis,Photophysical and Electronic Properties of New Red-to-NIR Emitting Donor–Acceptor Pyrene Derivatives

We synthesized new pyrene derivatives with strong bis(para-methoxyphenyl)amine donors at the 2,7-positions and n-azaacene acceptors at the K-region of pyrene. The compounds possess a strong intramolecular charge transfer, leading to unusual properties such as emission in the red to NIR region (700 nm), which has not been reported before for monomeric pyrenes. Detailed photophysical studies reveal very long intrinsic lifetimes of >100 ns for the new compounds, which is typical for 2,7-substituted pyrenes but not for K-region substituted pyrenes. The incorporation of strong donors and acceptors leads to very low reduction and oxidation potentials, and spectroelectrochemical studies show that the compounds are on the borderline between localized Robin-Day class-II and delocalized Robin-Day class-III species.     

Surface tension of liquid high-entropy equiatomic alloys of a Cu–Sn–Bi–In–Pb system

An experimental study of the temperature dependences of the surface tension of liquid high-entropy equiatomic alloys of a Cu–Sn–Bi–In–Pb system is conducted. Measurements are made within the temperature range of t _L to 1300°C in the mode of heating and subsequent cooling of a sample. Overcooling of a melt prior to crystallization is detected. The depth of overcooling grows along with the number of components in the melt, while the temperature coefficient of surface tension falls. The experimental results qualitatively interpreted within the concepts of the specific surface entropy of a liquid.     

Oligothiophene-Ring-Strapped Perylene Bisimides: Functionalizable Coaxial Donor–Acceptor Macrocycles

Aesthetic designs from nature enable new knowledge to be gained and, at the same time, inspire scientific models. In this context, multicomponent macrocycles embody the advantage of precisely positioning the structural units to achieve efficient communication between them. However, the construction of a functionalizable macrocycle for ultrafast charge separation and stabilization has not been attempted. Herein, we report the synthesis, crystal structure, and transient absorption of a new functionalizable macrocycle consisting of an oligothiophene-ring-strapped perylene bisimide. Transient absorption results point to a sequential improvement in charge separation and stabilization from the macrocycle to the corresponding linear dimer and 2D polymer due to the unique design. Our macrocycle design with a supportive spatial arrangement of the donor and acceptor units will inspire the development of more complex synthetic systems with exciting electron-transfer and charge-separation features.     

Phase diagrams of a condensed decane–eicosane–cyclododecane system

An n-eicosane–cyclododecane–n-decane system related to eutectic-type systems is investigated by means of differential thermal analysis. The eutectic alloy with melting point of–33.8°C contains 2.8 wt % of n-eicosane, 89.2 wt % of n-decane, and 8.0 wt % of cyclododecane.     

Towards a definition of almost–equienergetic graphs

The energy $E(G)$ of a graph $G$ , a quantity closely related to total $\pi $ -electron energy, is equal to the sum of absolute values of the eigenvalues of $G$ . Two graphs $G_a$ and $G_b$ are said to be equienergetic if $E(G_a)=E(G_b)$ . In 2009 it was discovered that there are pairs of graphs for which the difference $E(G_a)-E(G_b)$ is non-zero, but very small. Such pairs of graphs were referred to as almost equienergetic, but a precise criterion for almost–equienergeticity was not given. We now fill this gap.     

Solution-based fabrication of a graphene–ZnO nanocomposite

Graphene-based composites represent a new class of materials with potential for many applications. Graphene can be attached to a metal, a semiconductor, or any polymer. In this work, our approach was to attach graphene to a well-known semiconductor, ZnO. We synthesized graphene–ZnO composites by a simple, low-cost, environmentally friendly solvothermal method, carrying out the reaction in different conditions in order to discover the optimum condition, and also to obtain a high-quality product. Our research demonstrated that the optimum temperature to obtain a high-quality product is 180 °C for 20 h. All obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy, electron dispersion spectrometry, X-ray photoelectron spectrometry, Raman spectroscopy, Fourier transform infrared spectrometry, UV–visible spectrophotometry, and thermogravimetric analysis. The XRD confirmed that the crystal structure of the ZnO in the nanocomposite was wurtzite type. The prepared composite was stable to 800 °C with its 80 % weight.     

Synthesis of a mitomycin C–lexitropsin hybrid

We have constructed hybrid drugs where mitomycin C is linked to the N-methylpyrrole carboxamide framework present in lexitropsins. The coupling reactions leading to these products are efficient and the yields are very high. An interesting spectroscopic feature of these hybrids is the red shift observed in the UV–vis spectrum. Although DFT calculations indicate the possible existence of complexes formed during the coupling reactions, these complexes were not detected. The only species produced and isolated were the mitomycin C-mono- and bis-N-methyl pyrrole conjugates.     

CFD analysis of a TG–DSC apparatus

A ThermoGravimetric analyser with differential scanning calorimetry (TG–DSC) has been studied during the fusion of an indium sample using both an experimental procedure and a CFD simulation. To do so, a CAD model of the real device was built and meshed in detail, in order to take into account the small scale processes which occur inside the crucibles. Several theoretical models, some previously existing in the CFD software used and others developed ad hoc, were applied to simulate the whole facility. Therefore, realistic boundary conditions and a PID-based control system already developed for previous studies had to be used. The validation of the CFD model was done by comparing the outcome of the resulting simulation to the results obtained by experimental procedure in a case where natural convection is the main heat and mass transfer mechanism. This comparison was made for two different heating rates inside the furnace. Typical characteristics of phase change process inside a TG-DSC as thermal lag, onset temperature or heat flow exchange during the fusion could be analysed. As well, a more detailed approach to physical phenomena taking place inside the furnace could be done, since CFD simulations allow to obtain data which is not achievable experimentally. Besides, a valid CFD model for a TG-DSC could be later used in further CFD simulations.     

Oxidative dehydrogenation of ethane over a Mo–V–Nb–Te–O mixed-oxide catalyst in a cyclic mode

The oxidative dehydrogenation of ethane (ODE) into ethylene over a Mo–V–Nb–Te–O mixedoxide catalyst in a cyclic mode with alternate feeding of ethane and air has been investigated. The amount of oxide-phase oxygen involved in the reaction has been estimated by titrating the oxygen of the active phase of the catalyst with ethane. The reactivity of this oxygen increases with an increasing temperature. The amount active oxygen involved in ODE at 360–400°C is 0.2–0.6 mmol/g.     

Non-isothermal crystallization kinetics of a Si–Ca–P–Mg bioactive glass

In this work, the crystallization process of a SiO₂–3CaO·P₂O₅–MgO glass was studied by non-isothermal measurements using differential thermal analysis carried out at various heating rates. X-ray diffraction at room and high temperature was used to identify and follow the evolution of crystalline phases with temperature. The activation energy associated with glass transition, (E _g), the activation energy for the crystallization of the primary crystalline phase (E _c), and the Avrami exponent (n) were determined under non-isothermal conditions using different equations, namely from Kissinger, Matusita & Sakka, and Osawa. A complex crystallization process was observed with associated activation energies reflecting the change of behavior during in situ crystal precipitation. It was found that the crystallization process was affected by the fraction of crystallization, (x), giving rise to decreasing activation energy values, E _c(x), with the increase of x. Values ranging from about 580 kJ mol^?1 for the lower crystallized volume fraction to about 480 kJ mol^?1 for volume fractions higher than 80 % were found. The Avrami exponents, calculated for the crystallization process at a constant heating rate of 10 °C min^?1, increased with the crystallized fraction, from 1.6 to 2, indicating that the number of nucleant sites is temperature dependent and that crystals grow as near needle-like structures.