Donor Position Research Articles

Steric effects and electronic manipulation of multiple donors on S0/S1 transition of Dn-A emitters

Multiple donor-acceptor (D-A) combinations represent a promising category of thermally activated delayed fluorescence (TADF) materials, offering potential for superior efficiency and stability. However, current systems are predominantly composed of limited donor groups, primarily carbazole-based derivatives. In this work, we developed a series of D-A type materials incorporating helical π-expanded carbazole (CzNaph) and 7H-dinaphtho[1,8-bc:1′,8′-ef]azepine (AzNaph), alongside traditional carbazole, ranging from mono- to tetra-substituted configurations (Dn-A). Through systematic investigation of geometric and electronic structures, the number and positioning of multiple donors are confirmed with significant manipulations on charge transfer characteristics and the S1 state via steric effects. Density functional theory (DFT) calculations reveal that varying the number of π-extended donors within the acceptor framework produces emission colors from ultraviolet to red, providing a diverse range of emitters. Furthermore, the reduced reorganization energy of S1 observed in tetra-substituted Cz and CzNaph, as well as MonoAzN, indicates lower structural relaxation, highlighting these materials' potential as stable luminescent candidates. This study underscores the importance of diverse composing units in achieving efficient and stable TADF emitters with multiple and hetero-donor configurations.

Regioisomerism vs Conformation: Impact of Molecular Design on the Emission Pathway in Organic Light-Emitting Device Emitters.

Despite the design and proposal of several new structural motifs as thermally activated delayed fluorescent (TADF) emitters for organic light-emitting device (OLED) applications, the nature of their interaction with the host matrix in the emissive layer of the device and their influence on observed photophysical outputs remain unclear. To address this issue, we present, for the first time, the use of up to four regioisomers bearing a donor-acceptor-donor electronic structure based on the desymmetrized naphthalene benzimidazole scaffold, equipped with various electron-donating units and possessing distinguished conformational lability. Quantum chemical calculations allow us to identify the most favorable conformations adopted by the electron-rich groups across the entire pool of regioisomers. These conformations were then compared with conformational changes caused by the interaction of the emitter with the Zeonex and 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) matrices, and the correlation with observed photophysics was monitored by UV-vis absorption and steady-state photoluminescence spectra, combined with time-resolved spectroscopic techniques. Importantly, a CBP matrix was found to have a significant impact on the conformational change of regioisomers, leading to unique TADF emission mechanisms that encompass dual emission and inversion of the singlet-triplet excited-state energies and result in the enhancement of TADF efficiency. As a proof of concept, regioisomers with optimal donor positions were utilized to fabricate an OLED, revealing, with the best-performing dye, an external quantum emission of 11.6%, accompanied by remarkable luminance (28,000 cd/m2). These observations lay the groundwork for a better understanding of the role of the host matrix. In the long term, this new knowledge can lead to predicting the influence of the host matrix and adopting the structure of the emitter in a way that allows the development of highly efficient and efficient OLEDs.

Tailoring the donor moieties in TPA‐based organic dyes for efficient photovoltaic, optical and nonlinear optical response properties

AbstractThe current study reports tailoring the electronic donor structures of organic dyes to modify their optical and nonlinear optical (NLO) response properties. Five (5) tri‐phenyl amine (TPA) based Donor‐π‐Acceptor (D‐π‐A) organic dyes with the codes ICAA1, ICAA2, ICAA3, ICAA4, and ICAA5 were designed and investigated for their optical and NLO properties using quantum chemical methods. Optical and NLO properties of these dyes were studied by CAM‐B3LYP method and 6‐311G* basis set. The focus has been on the impact of adding secondary donors and shifting their substitutions at ortho (o), meta (m) and para (p) positions. Among all designed compounds, ICAA4 showed the highest amplitude of average third‐order NLO polarizability <γ>, which is calculated to be 1316 × 10−36 esu. Time‐dependent Density Functional Theory (TD‐DFT) method was used to determine how a change in the position of the donor affected the excitation energy (Eg) and NLO response properties. The findings showed that changing the position of the secondary donor results in a red shift among absorption spectra as well as the increase in their NLO responses. Complete process of intramolecular charge transfer (ICT) has been investigated in terms of different optical parameters such as frontier molecular orbitals (FMOs), molecular electrostatic potentials (MEPs), transition density matrix (TDMs), density of states (DOS), electron density difference (EDD), and natural bond orbital (NBO) analysis. Our calculations for study of ICT process indicate that p‐position of methoxy group performs better among all other positions and even it has better NLO response properties than the compound with three collective methoxy groups. The calculated Voc values of all designed molecules range from 1.09 to 1.30, all of them are positive while their ΔGinject is found to be in the range of −0.87 to −1.79 eV indicating their decent potential for photovoltaic applications. The studied optical, NLO and photovoltaic parameters illustrated that ICAA1 to ICAA5 are appropriate molecules not only for NLO applications but also for efficient photovoltaic purposes.

Rational molecular design of efficient yellow-red dendrimer TADF for solution-processed OLEDs: a combined effect of substitution position and strength of the donors

AbstractThe development of high-performance solution-processed red organic light-emitting diodes (OLEDs) remains a challenge, particularly in terms of maintaining efficiency at high luminance. Here, we designed and synthesized four novel orange-red thermally activated delayed fluorescence (TADF) dendrimers that are solution-processable: 2GCzBP, 2DPACzBP, 2FBP2GCz and 2FBP2DPACz. We systematically investigated the effect of substitution position and strength of donors on the optoelectronic properties. The reverse intersystem crossing rate constant (kRISC) of the emitters having donors substituted at positions 11 and 12 of the dibenzo[a,c]phenazine (BP) is more than 10-times faster than that of compounds substituted having donors substituted at positions 3 and 6. Compound 2DPACzBP, containing stronger donors than 2GCzBP, exhibits a red-shifted emission and smaller singlet-triplet energy splitting, ΔEST, of 0.01 eV. The solution-processed OLED with 10 wt% 2DPACzBP doped in mCP emitted at 640 nm and showed a maximum external quantum efficiency (EQEmax) of 7.8%, which was effectively maintained out to a luminance of 1,000 cd m−2. Such a device∙s performance at relevant display luminance is among the highest for solution-processed red TADF OLEDs. The efficiency of the devices was improved significantly by using 4CzIPN as an assistant dopant in a hyperfluorescence (HF) configuration, where the 2DPACzBP HF device shows an EQEmax of 20.0% at λEL of 605 nm and remains high at 11.8% at a luminance of 1,000 cd m−2, which makes this device one of the highest efficiency orange-to-red HF SP-OLEDs to date.

Binding energies of shallow donors in polar ZnO/ZnBeO quantum well

This study examines a single wurtzite ZnO/ZnBeO quantum well structure oriented in the polar c-direction. The focus is on investigating the binding energies associated with an impurity donor atom within this system. To achieve this, a self-consistent solution to the Schrödinger and Poisson equations is obtained using the finite difference method. The framework employed involves the effective mass and envelope function approximations. The impurity is represented using a hydrogenic-type wave function, and donor binding energies are determined via a variational approach. The research analyzes the binding energies of the 1s and 2p± states, along with the transition energy between them. These quantities are explored as functions of the well width and Be concentration, considering donor positions at the right and left interfaces as well as at the well’s center. Furthermore, the impact of an external magnetic field oriented along the growth direction is assessed, spanning up to 10T, in order to quantify changes in the binding energies. The presence of a built-in electric field induces an asymmetric band profile and a triangular well configuration. This asymmetry results in a loss of symmetry within the binding energy curves. Ultimately, the investigation culminates in the computation of the oscillator strength governing transitions between the donor states. When the donor is situated at the right interface, the energy values remain relatively constant as the well width increases, and the oscillator strength values demonstrate a consistent linear rise.

Attractive acceptor-acceptor interactions in self-complementary quadruple hydrogen bonds for molecular self-assembly.

Molecular self-assembly provides the means for creating large supramolecular structures, extending beyond the capability of standard chemical synthesis. To harness the power of self-assembly, it is necessary to understand its driving forces. A potent method is to exploit self-complementary hydrogen bonding, where a molecule interacts with its own copy by suitable positions of hydrogen-bond donor (D) and acceptor (A) groups. With four hydrogen bonds, there are two possible self complementary patterns: the DDAA/AADD and the DADA/ADAD motifs. Of these, the DDAA pattern is usually more stable. The traditional explanation assumes that the secondary interactions between equal groups, that is, between donors (D⋯D) or acceptors (A⋯A), are repulsive. DDAA arrays would then have two, and DADA arrays six repulsive interactions. Here, using high-end quantum chemical analysis, we show that contrary to the traditional explanation, the secondary A⋯A interactions are, in fact, attractive. We revise the model of secondary interactions accordingly.

A stereoselective organocatalyzed C-glycosylation of indole: implications of acceptor–catalyst–donor interactions

A stereoselective organocatalyzed C-glycosylation of indole is presented, featuring the plausible formation of a catalyst–acceptor complex and a crucial H-bond between the N–H group of indole and the oxygen atom at the C6 position of the sugar donor.

An Integrated Access and Backhaul Approach to Sustainable Dense Small Cell Network Planning

Integrated access and backhaul (IAB) networks offer transformative benefits, primarily their deployment flexibility in locations where fixed backhaul faces logistical or financial challenges. This flexibility is further enhanced by IAB’s inherent ability for adaptive network expansion. However, existing IAB network planning models, which are grounded in the facility location problem and are predominantly addressed through linear programming, tend to neglect crucial geographical constraints. These constraints arise from the specific deployment constraints related to the positioning of IAB donors to the core network, and the geographic specificity required for IAB-node placements. These aspects expose an evident research void. To bridge this, our research introduces a geographically aware optimization methodology tailored for IAB deployments. In this paper, we detail strategies for both single-hop and multi-hop situations, concentrating on IAB donors distribution and geographical constraints. Uniquely in this study, we employ the inherent data rate limitations of network nodes to determine the maximum feasible hops, differing from traditional fixed maximum hop count methods. We devise two optimization schemes for single-hop and multi-hop settings and introduce a greedy algorithm to effectively address the non-convex multi-hop challenge. Extensive simulations across various conditions (such as diverse donor numbers and node separations) were undertaken, with the outcomes assessed against the benchmark of the single-hop scenario’s optimal solution. Our findings reveal that the introduced algorithm delivers efficient performance for geographically constrained network planning.

Electrocatalytic Synthesis of 1,2-Dioxolanes from Tetrasubstituted Donor–Acceptor Cyclopropanes

AbstractAn electrochemical method for the synthesis of 3,3,5,5-tetrasubstituted 1,2-dioxolanes from donor–acceptor cyclopropanes with quaternary donor positions is described. This catalyst-free strategy delivers radical cations after C(sp3)–C(sp3) cleavage by direct anodic oxidation of the strained carbocycle. A broad scope with regard to the cyclopropanes employed in the reaction is presented. Additionally, we propose a plausible mechanism for the reaction.

High-efficiency long-wavelength NIR iridium complexes constructed by extending rigid coordination and optimizing peripheral donor position to break cocoon into butterfly

Due to the non-radiative decay of excited states, it is extremely complicated for iridium (III) complexes to simultaneously harvest high-efficiency and long-wavelength emission in the near-infrared (NIR) region based on the energy-gap law. In order to address this issue, we designed and synthesized two butterfly-type iridium(III) complexes of (PyPz-TPA)2Ir(acac) and (PyQl-TPA)2Ir(acac), in which pyrene-pyrazine (PyPz) and pyrene-quinoxaline (PyQl) are respectively used as the rigid C^N bidentate coordinated cocoons, peripherally with two triphenylamine (TPA) units at 4, 5-positions. Their photophysical, electrochemical and electroluminescent properties are primarily investigated. It is found that the (PyQl-TPA)2Ir(acac) presents stronger spin-orbital coupling effect, a smaller ΔEST energy difference, and lower reorganization energy than (PyPz-TPA)2Ir(acac) by selecting rigid pyrene-quinoxaline coordination and optimizing peripheral TPA position. Furthermore, the (PyQl-TPA)2Ir(acac)-doped OLEDs exhibit a red-shifted NIR emission peaked at 784 nm with a record external quantum efficiency of 5.42% using CBP as host matrix by solution process, which is a rare representation to shrink the limitation of energy-gap law in NIR region for iridium(III) complexes. This study provides a feasible strategy to construct high-efficiency NIR-emitting iridium(III) complexes by an artfully motivated strategy of extending and breaking the C^N coordinate cocoon into butterfly.

The Effect of a Single Off-Center Shallow Donor Atom on the Binding Energy and Diamagnetic Susceptibility in a GaAs Horn Torus Quantum Dot

In this work, we have studied an electron confined in a GaAs Horn torus quantum dot in the presence of a shallow donor impurity. Using the effective mass approximation and by considering an infinite confinement potential, the Schrödinger equation was calculated by the finite difference method. The electron-impurity binding energy and the diamagnetic susceptibility are studied for different geometric sizes of the Horn torus. In addition, the effect of the radial and angular positions of the shallow donor impurity on the binding energy and the diamagnetic susceptibility are examined. The results show that the binding energy is much higher at small sizes of the nano system. Also, the diamagnetic susceptibility exhibits a symmetric behavior as a function of the angular position of the shallow impurity donor unlike that when the impurity moves radially. The influences of these parameter variants help us to better understand the effects of the size of the quantum dot and the position of the donor impurity, which improve the sensitive of the opto-electronic devices.

Stark Effect for Donors in Rolled-Up Quantum Well.

We calculate energies of shallow donors confined in a rolled-up quantum well in the presence of the electric field by solving numerically the Schrödinger equation in natural curvilinear coordinates. It is found that the curves of density of states (DOSs) are very sensitive to the variation of the donor position, the geometry of the spiral and the applied electric field value. Novel results for dependencies of donor's dipole moment and its polarizability on the electric field strength and its orientation, for different donor positions are presented. Additionally, we found that the anisotropic Stark effect of the first order provides in this structure a dependency of the polarizability on the external electric field in a spike-like shape, giving rise to a sharp variation of the dipole moment.

Spin-orbit interaction effect on a hydrogenic [formula omitted] centre in a three-dimensional asymmetric Gaussian GaAs quantum dot in a magnetic field

The binding energy of a hydrogenic neutral D0 complex situated in a three-dimensional asymmetric Gaussian GaAs quantum dot is studied incorporating the Rashba and Dresselhaus spin-orbit interactions and the effect of an external magnetic field by means of a variational method and its variation with respect to the quantum dot size, strength of the magnetic field, donor position and spin-orbit coupling strengths is calculated. The behavior of the magnetic susceptibility of the system is also investigated with respect to the magnetic field for different values of the quantum dot parameters.

Association of Socioeconomic Position With Racial and Ethnic Disparities in Survival After Lung Transplant

A recent National Academies of Sciences, Engineering, and Medicine study found that transplant outcomes varied greatly based on multiple factors, including race, ethnicity, and geographic location. They proposed a number of recommendations including studying opportunities to improve equity in organ allocation. To evaluate the role of donor and recipient socioeconomic position and region as a mediator of observed racial and ethnic differences in posttransplant survival. This cohort study included lung transplant donors and recipients with race and ethnicity information and a zip code tabulation area-defined area deprivation index (ADI) from September 1, 2011, to September 1, 2021, whose data were in the US transplant registry. Data were analyzed from June to December 2022. Race, neighborhood disadvantage, and region of donors and recipients. Univariable and multivariable Cox proportional hazards regression were used to study the association of donor and recipient race with ADI on posttransplant survival. Kaplan-Meier method estimation was performed by donor and recipient ADI. Generalized linear models by race were fit, and mediation analysis was performed. Bayesian conditional autoregressive Poisson rate models (1, state-level spatial random effects; 2, model 1 with fixed effects for race and ethnicity, 3; model 2 excluding region; and 4: model 1 with fixed effects for US region) were used to characterize variation in posttransplant mortality and compared using ratios of mortality rates to the national average. Overall, 19 504 lung transplant donors (median [IQR] age, 33 [23-46] years; 3117 [16.0%] Hispanic individuals, 3667 [18.8%] non-Hispanic Black individuals, and 11 935 [61.2%] non-Hispanic White individuals) and recipients (median [IQR] age, 60 [51-66] years; 1716 [8.8%] Hispanic individuals, 1861 [9.5%] non-Hispanic Black individuals, and 15 375 [78.8%] non-Hispanic White individuals) were included. ADI did not mediate the difference in posttransplant survival between non-Hispanic Black and non-Hispanic White recipients; it mediated only 4.1% of the survival difference between non-Hispanic Black and Hispanic recipients. Spatial analysis revealed the increased risk of posttransplant death among non-Hispanic Black recipients may be associated with region of residence. In this cohort study of lung transplant donors and recipients, socioeconomic position and region of residence did not explain most of the difference in posttransplant outcomes among racial and ethnic groups, which may be due to the highly selected nature of the pretransplant population. Further research should evaluate other potentially mediating effects contributing to inequity in posttransplant survival.

Toward Imaging Defect-Mediated Energy Transfer between Single Nanocrystal Donors and Single Molecule Acceptors.

Defect-mediated energy transfer is an energy transfer process between midgap electronic states in a semiconductor nanocrystal (NC) and molecular acceptors, such as fluorescent dye molecules. Super-resolution fluorescence microscopy represents an exciting technique for pinpointing the nanoscale positions of lattice defect sites in, for example, a micrometer-sized particle or thin film sample by spatially resolving the location of the acceptor dye molecules with nanometer resolution. Toward this goal, our group performed ensemble-level, time-resolved fluorescence spectroscopy measurements of ZnO NC/Alexafluor 555 (A555) mixtures and calculated that the emissive defect sites are located, on average, 0.5 nm from the NC surface [Nilsson Z. N.; J. Chem. Phys.2021, 154 ( (5), ), 054704]. However, ensemble-level measurements cannot spatially resolve the defect sites on single particles, nor can they distinguish between surface-adsorbed dye molecules that participate in the energy transfer (EnT) process from those that do not. In this work, we compared the photoluminescence intensity trajectories of 789 isolated, single ZnO NC donors to those of 73 non-specifically bound and five specifically bound ZnO NC/A555 pairs, where the donor and acceptor centroid positions were separated by a distance that was smaller than our localization precision (40 nm). We observed minor fluorescence intensity fluctuations in the donor and defect channels instead of clear anticorrelated intensity fluctuations, which could be explained by (1) the presence of multiple emissive defect sites per NC, (2) donor-acceptor separation distances slightly larger than the Förster radius (R 0 = 3.1 nm; defined as the distance at which EnT is 50% efficient), and/or (3) poor dipole-dipole coupling. The single molecule imaging methodology we developed, an alternating ultraviolet-visible excitation sequence combined with multicolor photon detection, successfully distinguishes specifically bound and non-specifically bound NC/dye pairs and can be applied to study a wide range of hybrid NC/dye energy transfer systems.

Efficient Solid‐State Emission Control by Positional Isomerism for Platinum(II) Complex with Donor–π–Acceptor Ligand

AbstractSquare‐planar platinum (Pt)(II) complexes have attracted considerable attention owing to their unique luminescent properties, and the development of facile methods to control them is very important. A series of Pt(II) complexes containing a donor–π–acceptor (D–π–A) isomer ligand (ortho‐, meta‐, and para‐position; Pt‐O, Pt‐M, and Pt‐P) is prepared to investigate the positional isomerism on the Pt(II) complex. In particular, the metal‐to‐ligand charge transfer and ligand intramolecular charge transfer characteristics are examined depending on the positional isomer and compared with the donor‐free Pt(II) complex. All Pt(II) complexes observe slightly red‐shifted emission within 10 nm in the order of Pt‐O < Pt‐M < Pt‐P. Experimental data and theoretical calculations show that the Pt(II) complex lowest unoccupied molecular orbital energy level is controlled systematically by the donor position dependency. In particular, the small perturbation of the electronic state by positional isomerism in the single molecule induces significant phosphorescence color disparities of more than 82 nm in the solid‐state emission spectra and aggregation‐induced emission. The intriguing phosphorescent behavior is explained by the ligand‐dependent macroscopic molecular array with the Hirshfeld analysis. Consequentially, this paper reports a facile emission control method by the D–π–A ligand positional isomerism in the Pt(II) complex.

Large permittivity, low loss and defect structure in (Nb, Zn) co-doped SnO2 ceramics studied through a combined experimental and DFT calculational method

Dielectric ceramics with high permittivity and low loss are widely used in electronic components and devices. In this study, (Nb, Zn) co-doped NbxZnySn1-x-yO2 with different doping levels and Nb/Zn ratios was designed to tune the defect structure toward the optimal dielectric performance. The lattice parameters firstly increased from x = y = 0.01 to 0.03 and then decreased, while the oxygen vacancy concentration decreased with doping. The co-doped sample with x = y = 0.02 exhibits stable permittivity up to 800 with an ultra-low loss tanδ ∼0.03 at 40 Hz. DFT calculation showed that the oxygen vacancy was formed with single-Zn doping and co-doping at low doping level, while the hole was generated at higher doping level. The achieved large permittivity and low loss of the sample are related to both Electron-Pinned Defect Dipoles (EPDD) and Hole-Pinned Defect Dipoles (HPDD) effects in the lattice, which was determined by the relative positions of donor and acceptor dopants.

Electro‐optical Properties of ZnSe Doped with Gd and (Ag,Gd) Phosphors

AbstractTo understand the position of donor‐ acceptor level and nature of electronic state of activators and co‐ activators, the photo luminescence (PL) and electroluminescence (EL) emission spectra of Znse: Gd and Zn Se: (Ag, Gd) phosphors, have been recorded at room temperature. The method of preparation of phosphors is described. Voltage and frequency dependence of electroluminescent has also b been described. The light output varies as been studied for a wide range of frequencies. It is observed that the EL emission spectra of these phosphors are shifted towards lower wavelength sides on increasing the field frequency.

Bir Ülke Neden Başka Bir Ülkeye Yardım Eder? Kalkınma Yardımlarının Ortaya Çıkışı, Gelişimi ve Donörlerin Motivasyonları

In addition to the development approaches they adopt, countries that are in the position of donor and provide development assistance may have different orientations according to the beneficiary country they are dealing with, the global conjuncture they are in, and the methods they prefer. These factors and many other factors constitute the motivation of donor countries to offer assistance. Herein, donors acting according to their national strategic priorities, donors taking positions according to their position in the global economic order, donors which display different attitudes according to the beneficiary country they deal with, and donors which evaluate development assistance in the context of international relations have different motivations. In the study, primarily, the concept of development assistance was conceptually discussed, and the theoretical foundations on which it is built were explained. Afterward, historical changes and transformations were discussed. The donor countries' motivation to offer assistance, which is the main focus of the study, was examined through the categorization of countries that have common characteristics among themselves. In this context, a heading was specifically opened for Turkey, and Turkey's history of development assistance was included as well. Moreover, the role played by international organizations, which are among the most important actors in this field, in the provision of assistance was also discussed under a separate heading.

Effect of cyano substituent on the functional properties of blue emitting Imidazo[1,2-a]pyridine derivatives

High fluorescence efficiency and balanced charge transportation in organic emitters are desirable characteristics for application in OLEDs. Generally, donor-acceptor compounds showing pronounced intramolecular charge transfer exhibit low fluorescence quantum yield. Here, we report D-A fluorophores containing CN-substituted 2-phenylimidazo[1,2-a]pyridine acceptor unit which exhibit good fluorescence characteristics. The positions of donors (triphenylamine/carbazole) and cyano substituents are respectively interchanged to get a series of isomers. All the fluorophores exhibit high fluorescence quantum yield (Фf≥ 0.70) and excellent thermal stability (Td10≥ 390 °C). A dye comprising triphenylamine unit at para-position of C2 phenyl ring exhibited red-shifted emission maxima with larger Stokes shift in the series. Moreover, all the isomers displayed excited-state solvatochromism attributable to the photo-induced intramolecular charge transfer between donors and cyano-imidazo[1,2-a]pyridine acceptor. Addition of the cyano group on imidazopyridine restrained the formation of aggregates in the solid-state and stabilized the lowest unoccupied molecular orbital. Among the all, doped devices constructed with 3 wt% of triphenylamine containing dye revealed excellent performance in the series with a maximum EQE of 6.9%, 2759 cd/m2 luminance, and CIE coordinates (0.16, 0.08) which is very close to the NTSC blue standard.