Host Compounds Research Articles

Trivalent Gd incorporated Zn2SiO4 phosphor material for EPR and luminescence investigations

Abstract Zn2SiO4:Gd3+ powder was obtained by the sol–gel preparation technique and then characterized by using Fourier-transform infrared spectroscopy and X-ray diffraction techniques. The sample exhibited photoluminescence in the ultraviolet spectral zone with a maximum emission wavelength of 314 nm. Ultraviolet emission in the range of 305–320 nm is also called ultraviolet-B emission. This UV range emission is used in lamps for skin treatment and phototherapy. The electron paramagnetic resonance spectrum recorded for the Zn2SiO4:0.015Gd3+ phosphor revealed g values of 3.46, 2.64, and 2.20, confirming the presence of Gd3+ ions in the small ligand field. Furthermore, Gd3+ ions attain tetrahedral symmetry in the prepared host compound.

Crystal Growth of Host Compound DED and Derivatives in Alkylbenzenes

Crystal Growth of Host Compound DED and Derivatives in Alkylbenzenes

A Cofacial Porphyrin Dimer Generated by Cooperative Zinc Ion Binding

Noncovalent cofacial porphyrin dimers have attracted interest due to their potential use as host materials or catalysts. In this study, we introduce a novel coordination‐directed cofacial porphyrin dimer from a meso‐tetraphenylporphyrin derivative modified with 2,2'bipyridine moieties at the meta positions of the phenyl groups. Spectroscopic investigation has shed light on the binding processes and the structure of the dimer in solution in detail. Initial Zn2+ ion binding to the porphyrin hinders the subsequent Zn2+ binding and the binding of the second porphyrin. However, once the dimer is formed, additional Zn2+ binding is notably enhanced, resulting in a pronounced S‐shaped binding curve. The detailed structure of the dimer in solution was established based on UV‐vis spectroscopy, various 1H NMR spectroscopy techniques and mass spectrometry. Simulations of ringcurrent‐induced chemical shift changes provided evidence for the face‐to‐face porphyrin structure with tetrahedral coordination of the bipyridine ligands. The X‐ray single crystal structure provided conclusive evidence for the structure of the face‐to‐face dimer, which remarkably resembles the model structure from the 1H NMR simulation. The stability of the dimer structure makes it promising for further exploration of this motif in developing new supramolecular structures and for their potential applications as host compounds and catalysts.

Origin of the Disparity between the Stability of Transmutated Mix-Cation and Mix-Anion Compounds

Transmutation is an efficient approach for material design. For example, ternary compound CuGaSe2 in chalcopyrite structure is a promising material for novel optoelectronic and thermoelectric device applications. It can be considered as formed from the binary host compound ZnSe in zinc-blende structure by cation transmutation (i.e., replacing two Zn atoms by one Cu and one Ga). While cation-transmutated materials are common, anion-transmutated ternary materials are rare, for example, Zn2AsBr (i.e., replacing two Se atoms by one As and one Br) is not reported. The physical origin for this puzzling disparity is unclear. In this work, we employ first-principles calculations to address this issue, and find that the distinct differences in stability between cation-transmutated (mix-cation) and anion-transmutated (mix-anion) compounds originate from their different trends of ionic radii as functions of their ionic state, i.e., for cations, the radius decreases with the increasing ionic state, whereas for anions, the radius increases with the increasing absolute ionic state. Therefore, for mix-cation compounds, the strain energy and Coulomb energy can be simultaneously optimized to make these materials stable. In contrast, for mix-anion systems, minimization of Coulomb energy will increase the strain energy, thus the system becomes unstable or less stable. Thus, the trend of decreasing strain energy and Coulomb energy is consistent in mix-cation compounds, while it is opposite in mix-anion compounds. Furthermore, the study suggests that the stability strategy for mix-anion compounds can be controlled by the ratio of ionic radii r 3/r 1, with a smaller ratio indicating greater stability. Our work, thus, elucidates the intrinsic stability trend of transmutated materials and provides guidelines for the design of novel ternary materials for various device applications.

Advancing MR‐TADF OLED Toward True‐Blue CIE Value via Asymmetric Host Materials with Amorphous Morphology

AbstractThe new host materials are reported to boost the multiple resonance‐induced thermally activated delayed fluorescence (MR‐TADF) based pure deep‐blue organic light emitting diodes (OLEDs) toward further shortening the emission full width at the half maximum (FWHM). Based on an unusual asymmetric design concept, two new host compounds Bz2cb and Bz2cbz are synthesized. Despite possessing a compact and rigid molecular packing in crystal, Bz2cbz shows pure amorphous morphology via vapor deposition, as confirmed by the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) analysis. Via incorporating a promising MR‐TADF emitter, ν‐DABNA‐O‐Me, into Bz2cb and Bz2cbz films, highly pure deep‐blue OLEDs are successfully demonstrated. Remarkably, the Bz2cbz device exhibits a 464 nm electroluminescence (EL) with narrow FWHM of 22 nm, accompanied by the reduction of the 0–1 vibronic sideband, and a maximum external quantum efficiency (EQEmax) of 28.2%, which, overall, reaches the true‐blue Commission Internationale de l'Eclairage coordinates (CIE) of (0.13, 0.07) and the high blue index of 253. The amorphous film formation turns out to be an important factor that is previously unrecognized to externally fine‐tune the MR‐TADF OLEDs toward even higher color purity.

Electronic, optical, and thermoelectric characteristics of (Ae)xFBiS2 (Ae=Sr, Ba, and x=1.7) layered materials useful in optical modulator devices

The recent discovery of superconductivity behavior in the mother BiS2-layered compounds has captivated the attention of several physicists. The crystal structure of superconductors with alternate layers of BiS2 is homologous to that of cuprates and Fe-based superconductors. The full-potential linearized augmented plane-wave (FP-LAPW) technique was utilized to investigate the electronic structures and density of states in the vicinity of the Fermi energy of SrFBiS2 and BaFBiS2 compounds under the electron carriers doping. The introduction of electron doping (carries doping) reveals that the host compounds SrFBiS2 and BaFBiS2 exhibit features indicative of superconductivity. This carrier doping of SrFBiS2 and BaFBiS2 compounds (electron-doped) has a significant impact on the lowest conduction states near the Fermi level for the emergence of the superconducting aspect. The electron doping modifies and induces changes in the electronic structures with superconducting behavior in (Ae)1.7FBiS2(Ae=Sr,Ba) compounds. A Fermi surface nesting occurred under the modification of electrons (carriers) doping in the host compounds SrFBiS2 and BaFBiS2. Furthermore, the optical characteristics of the carrier-doped SrFBiS2 and BaFBiS2 compounds are simulated. Due to the anisotropic behavior, the optical properties of these materials based on BiS2 demonstrate a pronounced polarization dependency. The starting point at zero photon energy in the infrared region is elucidated by considering the Drude features in the optical conductivity spectra of SrFBiS2 and BaFBiS2 compounds, when the electron carriers doping is applied. It was clearly noticed that the spin-orbit coupling (SOC) influences the electronic band structures, density of states, Femi surface, and optical features because of the heavy Bismuth atom, which may disclose fascinating aspects. Further, we conducted simulations to assess the thermoelectric properties of these mother compounds. The two BiS2-layered compounds could be suitable for practical thermoelectric purposes and are highlighted through assessment of electrical conductivity, thermal conductivity, Seebeck coefficient, and power factor. As a result, we propose that the mechanisms of superconducting behavior in BiS2 family may pave new avenues for investigating the field of unconventional superconductivity. It may also provide new insights into the origin of high-Tc superconductivity nature.

Electronic structure of BaBiO3 and electron–phonon coupling in K-doped superconducting bismuthate—A first-principles study

The electronic structure of BaBiO3 and Ba1−xKxBiO3, where x = 0.375, 0.4, and 0.425 is investigated using the density functional theory (DFT) in the generalized gradient approximation (GGA). The charge-density-wave (CDW) nature of the host compound is suppressed via potassium doping at Ba-site, resulting in the emergence of a metallic state. A strong hybridization between Bi-6s and O-A1g orbitals is observed in the electronic states near the Fermi level, particularly enhanced in the collapsed BiO6 octahedra of the undoped compound. The K-doped systems show stronger spσ hybridization than that of the host compound. The self-doped holes condensate in the antibonding combination of Bi-s and O-A1g orbitals of both the doped systems and in the collapsed octahedra of the undoped system. The exploration of lattice dynamics and electron–phonon coupling in Ba1−xKxBiO3 systems, elucidate that mainly the phonons corresponding to the oxygen bond stretching vibrations contribute most to the total electron–phonon coupling. The GGA-calculated electron–phonon coupling constants (λ) across varying K-concentrations inadequately account for experimental Tcs. The inclusion of long-range interactions through the HSE06 hybrid exchange–correlation functional substantially augments both λ and Tc, closely mirroring experimental observations and underscoring the crucial role of nonlocal correlations in these systems.

Evolutionary genomics of three agricultural pest moths reveals rapid evolution of host adaptation and immune-related genes.

Understanding the genotype of pest species provides an important baseline for designing integrated pest management (IPM) strategies. Recently developed long-read sequence technologies make it possible to compare genomic features of nonmodel pest species to disclose the evolutionary path underlying the pest species profiles. Here we sequenced and assembled genomes for 3 agricultural pest gelechiid moths: Phthorimaea absoluta (tomato leafminer), Keiferia lycopersicella (tomato pinworm), and Scrobipalpa atriplicella (goosefoot groundling moth). We also compared genomes of tomato leafminer and tomato pinworm with published genomes of Phthorimaea operculella and Pectinophora gossypiella to investigate the gene family evolution related to the pest species profiles. We found that the 3 solanaceous feeding species, P. absoluta, K. lycopersicella, and P. operculella, are clustered together. Gene family evolution analyses with the 4 species show clear gene family expansions on host plant-associated genes for the 3 solanaceous feeding species. These genes are involved in host compound sensing (e.g., gustatory receptors), detoxification (e.g., ABC transporter C family, cytochrome P450, glucose-methanol-choline oxidoreductase, insect cuticle proteins, and UDP-glucuronosyl), and digestion (e.g., serine proteases and peptidase family S1). A gene ontology enrichment analysis of rapid evolving genes also suggests enriched functions in host sensing and immunity. Our results of family evolution analyses indicate that host plant adaptation and pathogen defense could be important drivers in species diversification among gelechiid moths.

Host compounds based on the rigid 9,10-dihydro-9,10-ethanoanthracene framework: selectivity behaviour in mixed isomeric dichlorobenzenes

Two anthracenyl-derived host compounds (H2, H3), present in their inactive forms in the H2·o-DCB, 3(H2)·m-DCB and H3·m-DCB complexes (where DCB is dichlorobenzene), were shown to possess separation ability for these DCBs.

Photophysical properties of Pt(ii) complexes based on the benzoquinoline (bzq) ligand with OLED implication: a theoretical study.

In this study, we investigate photophysical properties of eight inorganic Pt(ii) complexes containing the bzq (benzoquinoline) ligand for OLED applications using high-level density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. We explore the radiative and non-radiative relaxation constants (k r, k nr), spin-orbit coupling (SOC) matrix elements, and spectral properties. To ensure compatibility between the host and guest compounds, we determine the HOMO and LUMO energy levels, as well as the triplet excitation energies of the selected systems, and evaluate their efficiency for OLED devices. Our findings indicate that all systems, except for 2a and 2b, exhibit a small S1-T1 energetic gap (ΔE ≤ 0.60 eV) and promising SOC matrix elements (25-93 cm-1), leading to a significant intersystem crossing (ISC) process. These complexes also show promising radiative relaxation rates (k r = ∼10-4 s-1) and high phosphorescent quantum yields (Φ > 30%). Thus, our results confirm that six out of the eight selected Pt(ii) complexes are promising candidates for use in the emitting layer (EML) of OLED devices as efficient green emitters.

Study on the host-guest interactions between tetramethyl cucurbit[6]uril and 2-heterocyclic-substituted benzimidazoles.

Cucurbit[n]urils (Q[n]s) are a class of supramolecular host compounds with hydrophilic carbonyl ports and hydrophobic cavities, which can selectively form host-guest inclusion complexes with guest molecules to change the properties of guest molecules. In this paper, tetramethyl cucurbit[6]uril (TMeQ[6]) was used as the host and three 2-heterocyclic substituted benzimidazole derivatives as the guests, and their modes of interaction were investigated using X-ray crystallography, 1H NMR spectrometry, and other analytical techniques. The results showed that TMeQ[6] formed a 1 : 1 host-guest inclusion complex with three guest molecules, and the binding process between them was mainly enthalpy-driven. The X-ray diffraction analysis indicated that the main driving forces for the formation of these three inclusion complexes included hydrogen bonding interactions and ion dipole interactions. There are two modes of interaction between G3 and TMeQ[6] in the liquid phase, indicating that the benzimidazole ring and heterocyclic substituents on the guest molecule compete with the cavity of TMeQ[6]. Besides, the addition of TMeQ[6] significantly enhanced the fluorescence of these guests and slightly improved their solubility.

Alternative separation strategy for o-/p-dichlorobenzene mixtures through supramolecular chemistry protocols

A pair of significant short contacts involving chlorine atom of the guest species and hydrogens of the host compound ((guest)C–Cl⋯H–C(host)) that facilitate the retention of the favoured guest species in the H·1.5(oDCB) complex.

Bidentate boron Lewis acids: synthesis by tin boron exchange reaction and host-guest complex formation.

Four bidentate boron Lewis acids based on the 1,8-diethynylanthracene backbone have been synthesized by a tin-boron exchange reaction with various chloroboranes, yielding the products in good to excellent yields. Complexation experiments of the host compounds with pyridine, pyrimidine and TMEDA demonstrated striking differences in terms of formation and solubility of the supramolecular adducts. The host-guest complexes were investigated by multinuclear NMR spectroscopy and structurally characterized by X-ray diffraction experiments, illustrating the adaptation of the host system upon adduct formation with different neutral guest molecules.

Inclusion of halobenzene in water-mediated hydrogen-bonded architectures built from a V-shaped host molecule

Water-mediated hydrogen-bonded structures were built from a disubstituted adamantane with dimethoxyphenol moieties, where halobenzenes were accommodated within the cavity of cyclic dimers composed of host compounds and waters.

Polydentate chalcogen bonding: anion trapping with a water-stable host compound carrying Se-CF3 functions.

Bidentate and tetradentate chalcogen bonding host systems with SeCF3 functions as σ-hole donors in close proximity at the alkyne functions of 1,8-diethynylanthracene and its syn-dimer were prepared in quantitative yield by tin-selenium exchange reactions of the corresponding trimethylstannyl precursors with ClSeCF3. The bidentate system shows chalcogen bonding interactions with THF, but does not bind halide ions. The tetradentate system cooperatively chelates chloride, bromide and iodide ions with its four CC-SeCF3 units by rotating the four σ-holes towards the halide ion. The structures of these halide ion adducts were determined by X-ray diffraction. The hydrobromide and -iodide salts of the ethyl derivative of Schwesinger's phosphazene superbase served as halide salts with very weakly coordinating cations.

Investigation of the hydrogen bonded host‧‧‧guest and guest‧‧‧guest interactions present in complexes of a polyaromatic wheel-and-axle host compound with dioxane, morpholine, piperidine and pyridine

1,4-Bis(diphenylhydroxymethyl)benzene (H), a host compound possessing wheel-and-axle geometry, was found to possess host ability for dioxane (DIO), morpholine (MOR) and piperidine (PIP), forming inclusion compounds with each one with 1:2 host:guest ratios. This observation prompted an investigation of the host behaviour in mixtures of these guest compounds but where pyridine (PYR) was also considered (PYR was reported earlier to also form a 1:2 complex with H). In mixtures, H demonstrated significant affinities for, more especially, MOR and PIP, while DIO and PYR were usually disfavoured guest species. Single crystal X-ray diffraction experiments revealed that MOR (a favoured guest species) interacted by means of three hydrogen bonds with both adjacent guest and host molecules, plausibly explaining the host preference for this guest species; each of DIO, PYR and PIP were involved in only one interaction of this type with H. Total energy calculations revealed that the host-guest molecular pairs involving preferred MOR and PIP possessed significantly lower energies than those with disfavoured DIO and PYR. Thermal analyses demonstrated that the complex containing the least favoured guest compound, H‧2(DIO), possessed the lowest thermal stability of the four complexes, but these experiments did not clearly explain the affinity of H for MOR.

Infrared spectroscopic and gravimetric analysis of the dicyclobutylaminemetal(II) tetracyanonickellate(II) host-aromatic guest complexes

M(cyclobutylamine)2Ni(CN)4 (M = Ni or Co) host and M(cyclobutylamine)2Ni(CN)4.nG (M = Ni or Co; cba = cyclobutylamine; G = benzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene and naphthalene; n=the number of guest) host-guest compounds were synthesized and characterized by infrared spectroscopy. The spectral results were found to be consistent with the structure of the Hofmann-dma-type hosts. The absorption and release studies of certain aromatic guests (benzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, and naphthalene) molecules in the host complexes were investigated by gravimetric and spectroscopic methods at room temperature. The liberation of guest molecule benzene against time has been examined. The structures of M(cyclobutylamine)2Ni(CN)4 host do not affect when the guest molecule is included and liberated. It is thought that the host compounds will guide as sorbents for isomeric separations.

What is TADF (thermally activated delayed fluorescence) compared to the mechanisms of FL (fluorescence), PH (phosphorescence), and TTA (triplet–triplet annihilation) based on a novel naphthalimide sulfonylphenyl derivative as a host?

One of the biggest challenges in the field of optoelectronics is to easily identify the mechanisms involved in light-emitting materials. There are several different mechanisms of emission, and the best known are fluorescence (FL), phosphorescence (PH), thermally activated delayed fluorescence (TADF), and triplet–triplet annihilation (TTA). In this study, simple ways to diagnose these mechanisms are presented with an example. N,N-di(benzenesulfonylphenyl)-N-(N-2-aminomethylpyridine-1,8-naphthalimide)amine is synthesized as a host compound due to its high HOMO-LUMO and ionization potential (IP) values and three emitters consisting of 50 wt% Bis (1phenylisoquinoline))(acetylacetonate)iridium(III) (Ir(piq)2(acac)), 10-(4-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine (DMAC-TRZ) and 1,1′-(2,5-Dimethyl-1,4-phenylene)dipyrene (DMPPP) were considered. Overall, the host compound, doped Ir(piq)2(acac) and doped DMPPP follow the mechanisms of FL, the combination of FL and PH, and the combination of FL and TTA, as the photoluminescence (PL) decay life time and the PL intensity increased with decreasing temperature. However, DMAC-TRZ doped with the host compound showed the TADF mechanism, as the PL decay lifetime and the PL intensity increase simultaneously with increasing temperature. In addition, the difference between the singlet excited state (S1) and the triplet excited state T1 (ΔEST) from the PL and PH spectra at 77 K for the spin-coated DMAC-TRZ-doped host show the lowest value in between the samples at 0.02 eV, and the reverse intersystem crossing (rISC) effect is activated. Moreover, the linear slopes of the power dependence analysis of the DMPPP-doped host were calculated to be 2.04 and 0.91, indicating that there are two components (photons) for this sample which is strong evidence for the TTA mechanism. Taking into account the synthesized host compound, (Ir(piq)2(acac):host), (DMAC-TRZ:host) and (DMPPP:host) as emitter layers, the organic light emitting diodes (OLEDs) were fabricated via solution processing, and the TADF OLED exhibited the highest efficiency among the other OLEDs.

Computational investigation of the structures, properties, and host‐guest chemistry of prism[n]arenes

AbstractThe discovery of new and functional macrocyclic host compounds is an important part of supramolecular chemistry. Since the experimental synthesis, prism[n]arenes (Pr[n]As), a class of naphthol‐based macrocyclic arenes, have attracted much attention. In this work, from the perspective of theoretical calculation and research, Pr[n]As (n = 4 ~ 7) were studied by density functional theory (DFT) calculations and molecular dynamics (MD) simulations. The prismatic configuration isomers, electronic structures, absorption spectra, and host‐guest chemistry were discussed thoroughly. DFT calculation results showed that 1,5‐, 3,7‐, and “hybrid” 15,37‐Pr[n]As were the most representative configurations with the rigid prismatic molecular skeleton. Based on time‐dependent density functional theory (TD‐DFT), the absorption spectra of Pr[n]As were all in the range of ultraviolet light which were mainly attributed to π‐π* transitions. The molecular cavities of Pr[n]As were electron‐rich and capable of accommodating a variety of cations or electron‐conjugated molecules. MD simulation results showed that a Pr[n]A molecule was able to capture the guest molecule into its molecular cavity and maintain in the state of equilibrium in solvents.

What Is More Important to Host-Seeking Entomopathogenic Nematodes, Innate or Learned Preference?

Entomopathogenic nematodes (EPNs), small soil-dwelling non-segmented roundworms, are obligate parasites of insects and commonly used in agriculture for biological control of insect pests. For successful reproduction, EPNs must identify, move towards, and successfully infect a suitable insect host in a chemically complex soil environment. EPNs can have innate host insect preferences and can be attracted to semiochemicals associated with that host. They can also develop strong learned preferences for chemical signals associated with the presence of a host, such as herbivory-induced volatiles. We hypothesized that simultaneous manipulation of innate and learned preferences could result in increased biological control services of EPNs in agriculture. Separate cohorts of the EPN Steinernema diaprepesi were raised on two insect hosts, Galleria mellonella and Tenebrio molitor, for multiple generations until the nematodes in a dual-choice olfactometer exhibited preference for the host they were reared on. Subsequently, the two strains of nematodes were imprinted on three plant-produced terpenoids of agricultural significance: pregeijerene, β-caryophyllene, and α-pinene. After exposure to one of the plant compounds, the behavior of the EPNs was assayed in an olfactometer where the two host insects were presented with and without the plant compounds. We found that plant volatile exposure increased the infection rate of the nematodes, and some host–compound combinations proved to be attractive, but other combinations appeared to become repellent. These results indicate that learned preference is neither subordinate nor superior to innate preference, and that infection efficiency can vary with compound exposure and insect host.