WoS İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/394
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Article Citation - WoS: 13Citation - Scopus: 11Understanding the Effect of Symmetry Breaking on Plasmon Coupling From TDDFT(Amer Chemical Soc, 2021-05-26) Alkan, Fahri; Aikens, Christine M.We perform a time-dependent density functional theory (TDDFT) investigation for the optical properties of nanorod assemblies for different sizes (Ag-10, Ag-59, and Ag-139), interparticle distances, and orientations with a focus on the effect of symmetry breaking via an angle on plasmon coupling. For the model systems, the angle (theta) between the particles is varied between 0 and 180 degrees, where theta = 0 degrees and theta = 180 degrees correspond to symmetric side-by-side and end-to-end orientations of the nanorods, respectively. Our analysis reveals that for a sufficiently large interparticle distance (r > 0.7 nm), where the wave-function overlap between monomers is negligible, TDDFT results agree quite well with the predictions of the dipole-dipole interaction model for the intensity of the different modes of coupled plasmons. For smaller gap distances (0.4-0.5 nm), a charge-transfer plasmon (CTP) mode occurs for the symmetry broken case of the Ag-10 dimer. For the assemblies of larger nanorods, however, the CTP mode is predicted to be less pronounced, especially for the cases where the deviation from the end-to-end geometry is larger than 30 degrees. The orbital overlap and configuration-interaction analyses show that these results are related to the fact that the relative overlap strength between monomeric energy levels is significantly reduced for symmetry-broken orientations of larger nanorods.Article Citation - WoS: 19Citation - Scopus: 19Understanding and Tailoring Excited State Properties in Solution-Processable Oligo(p-Phenyleneethynylene)s: Highly Fluorescent Hybridized Local and Charge Transfer Character via Experiment and Theory(Amer Chemical Soc, 2021-10-13) Usta, Hakan; Cosut, Bunyemin; Alkan, FahriRod-shaped oligo(p-phenyleneethynylene) (OPE) offers an attractive p-framework for the development of solution-processable highly fluorescent molecules having tunable hybridized local and charge transfer (HLCT) excited states and (reverse) intersystem crossing ((R)ISC) channels. Herein, an HLCT oligo(p-phenyleneethynylene) library was studied for the first time in the literature in detail systematically via experiment and theory. The design, synthesis, and full characterization of a new highly fluorescent (Phi(PL-solution) similar to 1) sky blue emissive 4',4 ''-((2,5-bis((2-ethylhexyl)oxy)-1,4-phenylene)bis(ethyne-2,1-diyl))bis(N,N-diphenyl-[1,1'-bi-phenyl]-4-amine) (2EHO-TPA-PE) was also reported. The new molecule consists of a D'-Ar-pi-D-pi-Ar-D' molecular architecture with an extended pi-spacer and no acceptor unit, and detailed structural, physicochemical, single-crystal, and optoelectronic characterizations were performed. A high solid-state quantum efficiency (Phi(PL-solution) similar to 0.8) was achieved as a result of suppressed exciton-phonon/vibronic couplings (no pi-pi interactions and multiple (14 per dimeric form) strong C-H center dot center dot center dot pi interactions). Strong solution-phase/solid-state dipole-dependent tunable excited state behavior (local excited (LE) -> HLCT -> charge transfer (CT)) and decay dynamics covering a wide spectral region were demonstrated, and the CT state was observed to be highly fluorescent despite extremely large Stokes shift (similar to 130 nm)/fwhm (similar to 125 nm) and significant charge separation (0.75 charge.nm). Employing the Lippert-Mataga model, along with detailed photophysical studies and TDDFT calculations, key relationships between molecular design-electronic structure-exciton characteristics were elucidated with regards to HLCT and hot exciton channel formations. The interstate coupling between CT and LE states and the interplay of this coupling with respect to medium polarity were explored. A key relationship between excited-state symmetry breaking process and the formation of HLCT state was discussed for TPA-ended rod-shaped OPE p-systems. (R)ISC-related delayed fluorescence (tau similar to 2-6 ns) processes were evident following the prompt decays (similar to 0.4-0.9 ns) both in the solution and in the solid-state. As a unique observation, the delayed fluorescence could be tuned and facilitated via small dielectric changes in the medium. Our results and the molecular engineering perspectives presented in this study may provide unique insights into the structural and electronic factors governing tunable excited state and hot-exciton channel formations in OPEs for (un)conventional solution-processed luminescence applications.Article Citation - WoS: 1Citation - Scopus: 1Osmotic-Pressure Nematic Ordering in Suspensions of Laponite and Carboxy Methyl Cellulose(Amer Chemical Soc, 2020-10-12) Xu, Peicheng; Yazici, Ahmet F.; Erdem, Talha; Lekkerkerker, Henk N. W.; Mutlugun, Evren; Eiser, ErikaLaponite is a synthetic clay that is known to form gels in aqueous suspensions at low concentrations (0.01 g/cm(3)) Although it is expected to form lyotropic liquid crystals, such phases usually do not form, as a consequence of laponite's tendency to form gels at concentrations below the threshold for liquid crystal formation. Here we show that macroscopic, birefringent phases of laponite can be prepared through osmotic compression of a laponite solution by an aqueous solution of carboxy methyl cellulose (CMC). We present polarization imaging studies showing how the initially dilute, isotropic laponite phase shrinks while developing typical birefringence colors between crossed polarizers. Using the MichelLevy interference charts, we were able to extract the refractive index and orientation of the laponite nanodisks in the compressed region. Our observations allow us to propose a tentative state diagram, indicating the concentration regions for which we obtain optically anisotropic gels.Article Citation - WoS: 2Citation - Scopus: 2Light-Controlled Electrostatic Self-Assembly of Quantum Dots(Amer Chemical Soc, 2025-04-11) Akrema; Phul, Ruby; Yazici, Ahmet Faruk; Senel, Zeynep; Erdem, TalhaElectrostatic self-assembly is one of the important self-assembly mechanisms that found use in optoelectronics. Although this method enables realizing unconventional architectures, producing complicated architectures in large areas requires local control over the self-assembly process. One of the ways to achieve this control is to provide enough kinetic energy to the self-assembling nanoparticles so that they can escape electrostatic attraction. We hypothesize that this energy can be delivered to the nanoparticles by treating them with light that can be absorbed by the particles. Here, we test this idea to tailor the electrostatic self-assembly of semiconductor quantum dots (QDs) using a laser. Employing fluorescence and atomic force microscopy, we demonstrate that the QDs are not attached to the substrate in regions where they are exposed to light while they are coated in the absence of optical excitation. We further conduct theoretical analysis to show that elevated temperatures indeed allow the QDs to escape the electrostatic attraction of the charged polymers on the surface. We also demonstrate that increasing the temperature during the coating process without irradiating the sample gives similar results as the case when the sample was irradiated. Finally, we fabricate an uncoated region on the self-assembled QD film with dimensions of similar to 200 mu m x 0.5 cm to demonstrate the feasibility of our approach to control the bottom-up self-assembly. We believe that our results may pave the way for a cost-effective and sustainable approach for the fabrication of nanoelectronic and optoelectronic devices.Article Citation - WoS: 7Citation - Scopus: 7Giant Negative Linear Compressibility, Isosymmetric Phase Transition, and Breathing Effect in a 3D Covalent Organic Framework(Amer Chemical Soc, 2023-12-26) Erkartal, MustafaA set of remarkable piezo-mechanical properties, including isosymmetric phase transition, negative linear compressibility (NLC), and a breathing effect in a three-dimensional covalent organic framework (NPN-3), was uncovered using density functional theory. The pressure-induced first-order phase transition observed between 0.9 and 1 GPa is isosymmetric and irreversible. NPN-3 shows giant NLC along the c-axis (K-c = 42.04 TPa-1) prior to the phase transition. The high-density NPN-3-hd obtained as a result of the phase transition shows an exciting phase transition from a closed pore to an open pore under hydrostatic tensile pressure, similar to the breathing effect. These extraordinary piezo-mechanical attributes within NPN-3 can be attributed to the diamondoid (dia) topology, which is commonly found within flexible MOFs and COFs. Additionally, the remarkable adaptability of the tetraphenyl adamantane monomer to distinct conformations under pressure can be seen in these properties. These findings underscore the potential utility of COFs as materials for piezo-mechanical sensors and serve as a source of inspiration for further exploration into the intricate mechanical behaviors of COFs.Article Citation - WoS: 21Citation - Scopus: 21Efficient Forster Resonance Energy Transfer Donors of In(Zn)P/ZnS Quantum Dots(Amer Chemical Soc, 2017-01-26) Altintas, Yemliha; Talpur, Mohammad Younis; Mutlugun, Evren; Altlntas, YemlihaWe demonstrate a detailed investigation of the effect of the type and concentration of zinc precursor on the optical properties of In(Zn)P/ZnS quantum dots. We achieved up to 87% quantum yield along with 54 nm emission bandwidth for the green emitters with changing the concentration of the Zn precursors. Employing efficient green emitters as the donor species, we demonstrated an efficient Forster resonance energy transfer (FRET) couple of green and red emitting InP-based quantum dots. With a FRET efficiency level of 70.3% achieved (analyzed from the donor lifetime with and without an acceptor), we further demonstrated the enhancement of the acceptor emission nearly twofold due to the energy transfer. Our results provide new insights toward the understanding of the excitonic interactions among donor and acceptor quantum dots of the III-V family for light harvesting applications.Article Citation - WoS: 44Citation - Scopus: 46Highly Efficient Cd-Free Alloyed Core/Shell Quantum Dots With Optimized Precursor Concentrations(Amer Chemical Soc, 2016) Altintas, Yemliha; Talpur, Mohammad Younis; Unlu, Miray; Mutlugun, EvrenThe chemical composition, the emission spectral bandwidth, and photoluminescence quantum yield of a semiconductor quantum dot (QD) play an important role in the assessment of the performance of the applications related to the quantum dots. Quantum dots based on environmentally friendly compositions with high optical performance have been in demand for high-end technological applications. In this work, we propose and demonstrate a detailed synthesis approach for environmentally friendly and highly efficient InPZnS alloy/ZnS shell quantum dots. Following a systematic study of the ratio and type of the precursors involved, we achieved alloyed core shell InPZnS/ZnS QDs with tunable emission across the visible spectrum, having a record quantum efficiency up to 78% along with a full width at half-maximum as narrow as 45 nm. The effect of the systematic shell growth has been further investigated using time-resolved photoluminescence characterizations along with the observation of the suppression of the nonradiative decay channels, with the photoluminescence lifetime prolonged from 20.3 to 50.4 ns. The development of highly efficient and environmentally friendly QDs will pave the way for robust, sustainable optoelectronic applications.