Charge-transfer Crystals Research Articles

Charge-Transfer Complexes: Halogen-Doped Anthracene as a Case of Study.

Charge transfer (CT) crystals exhibit unique electronic and magnetic properties with interesting applications. We present a rational and easy guide which allows to foresee the effective charge transfer co-crystal production and that is based on the comparison of the frontier molecular orbital (MO) energies of a donor and acceptor couple. For the sake of comparison, theoretical calculations have been carried out by using the cheap and fast PM6 semiempirical Hamiltonian and pure HF/cc-pVTZ level of the theory. The results are then compared with experimental results obtained both by chemical (bromine and iodine were used as the acceptor) and electrochemical doping (exploiting an original experimental set-up by this laboratory: the electrochemical transistor). Infra-red vibrational experimental results and theoretically calculated spectra are compared to assess both the effective donor-acceptor (D/A) charge-transfer and transport mechanism (giant IRAV polaron signature). XPS spectra have been collected (carbon (1 s) and iodine (3d5/2)) signals, yielding further evidence of the effective formation of the CT anthracene:iodine complex.

Realizing the effect of s-block metals on a charge transfer crystal of indol-2-one for enhanced NLO responses with efficient energetic offsets.

Due to their unique photophysical properties, organic charge transfer crystals are becoming promising materials for next-generation optoelectronic devices. This research paper explores the impact of s-block metals on a charge transfer crystal of indol-2-one for enhanced nonlinear optical (NLO) responses with efficient energetic offsets. The study reveals that alkali metals can enhance NLO performance due to their free electrons. The Perdew-Burke-Ernzerhof functional of DFT with dispersion correction (D3) was used, and the λmax values ranged between 596 and 669nm, with the highest value for dichloromethane (DCM). Leveraging the unique properties of metals allowed for the development of nonlinear optical materials with improved performance and versatility. Softness (σ) values provide insight into electron density changes, with higher values indicating a greater tendency for changes and lower values indicating the opposite. The NLO results for the chromophores MMI1-MMI6 show varying linear polarizability (< α0 >) along with their first (β0) and second (γ0) hyperpolarizabilities. Chromophore MMI4 stands out with the highest NLO performance, having two potassium (K) atoms. Its < α0 > , β0, and γ0 values of 4.19, 7.09, and 17.43 (× 10-24 e.s.u), respectively, indicate a significant enhancement in NLO response compared to the other chromophores. The transitions involving (O20)LP → (C3-N5)π* and (O19)LP → (N12-C13)π* exhibit the highest level of stabilization, followed by (O23)π → (C10-C11)π*, while (C6-N12)π → (C6-C7)π* shows the lowest level of stabilization for chromophore MMI4. The present research work is facile in its nature, and it can be helpful for synthetic scientist to design the new materials for uniting crystal properties with metal doping for efficient NLO devices.

Visualizing Noncovalent Interactions and Property Prediction of Submicron-Sized Charge-Transfer Crystals from ab-initio Determined Structures.

The charge-transfer (CT) interactions between organic compounds are reflected in the (opto)electronic properties. Determining and visualizing crystal structures of CT complexes are essential for the design of functional materials with desirable properties. Complexes of pyranine (PYR), methyl viologen (MV), and their derivatives are the most studied water-based CT complexes. Nevertheless, very few crystal structures of CT complexes have been reported so far. In this study, the structures of two PYRs-MVs CT crystals and a map of the noncovalent interactions using 3D electron diffraction (3DED) are reported. Physical properties, e.g., band structure, conductivity, and electronic spectra of the CT complexes and their crystals are investigated and compared with a range of methods, including solid and liquid state spectroscopies and highly accurate quantum chemical calculations based on density functional theory (DFT). The combination of 3DED, spectroscopy, and DFT calculation can provide important insight into the structure-property relationship of crystalline CT materials, especially for submicrometer-sized crystals.

Charge-lattice coupling effects in organic isomeric charge transfer crystals

One of the most important features of organic cocrystals is the interaction between electrons and lattices, which brings interesting physical phenomena. In this work, we prepared two isomeric crystals in which the isomeric donors are used to fabricate charge transfer crystals. Isomeric crystals present different electron–lattice coupling strengths to further affect the charge localization, which leads to different dielectric constants and fluorescence lifetimes. Furthermore, external magnetic field and electric field exhibit different tunability on the photoluminescence and dielectric constants of the isomeric cocrystals due to the significant differences in the coupling between the charge and lattice vibration. Overall, through fabricating isomeric organic crystals, neighbor molecular vibration dependence of electron–lattice coupling is studied, which provides a platform to further understand the lattice vibration dependent spin and optics.

Magneto-responsive optics in a chiral crystal with thermally triggered reversible phase transitions between chiral space groups.

Herein, a chiral charge transfer crystal that exhibits reversible phase transition between chiral space groups has been fabricated. When the phase switches from left-handed to right-handed chiral space group, more pronounced orbital angular momentum effects will be generated, where magneto-responsive optics are the opposite for chiral enantiomers. Moreover, circularly polarized light could enhance the chiral orbit of the crystal with the same spiral orientation to let spin have a better ability to resist external magnetic field. Thus, the magnetic field dependence of transmission and photoluminescence of chiral crystals are strongly dependent on the polarized state of incident light. Furthermore, by studying the coupling among spin, orbit, and circular photon, we obtained that the chiral orbit plays a key role in the coupling between the spin and circular photon. It is expected that this work could promote further exploration of organic chiral magneto-optical crystals in potential applications of sensing.

Dimerization Triggered Magnetoelectric Coupling Effect and Magnetic Anisotropy in Organic Ternary Crystals.

Developing a new universal strategy to design all organic ferromagnets or multiferroics with satisfactory properties always remains challenging. In this work, ternary charge transfer crystals are fabricated to realize organic multiferroic magnetoelectric coupling effect. Through incorporating the third component into binary crystals, a dimerization between neighbor donor and acceptor is induced to form a lattice symmetry breaking, where a nonpolar to polar phase transition is ensuing to lead to a dipolar polarization. Magnetic field can effectively tune the dipolar polarization to present a magnetoelectric coupling effect. Moreover, the introduction of the third component can result in a rearrangement in molecular configuration to modify the electron-phonon interaction. As a result, anisotropic magnetism is observed due to anisotropic electron-phonon coupling in ternary crystals. Overall, this study forecasts that incorporating an appropriate third component is a potential method for designing all organic multiferroics.

Switchable magnetic, dielectric, conductivity, and phase transition properties of charge-transfer crystals

The properties can be switched between different states and can be used in sensors, displays, and memory devices. In this study, two multi-functional switchable materials [C5-Pmim][Ni(mnt)2] (1) and [C6-Hmim][Ni(mnt)2] (2) (where mnt2-= maleonitriledithiolate, C5-Pmim = 1-pentyl-3-methylimidazolium, and C6-Hmim = 1-hexyl-3-methylimidazolium) have been designed and synthesized, which has segregated cation and anion stacks in the crystal structure. 1 shows two-step switchable dielectric transition with a thermal hysteresis loop accompanying structure phase transition. Dielectric transition of 1 can be attributed to the reorientation of the polar cations and crystal to mesophase transition. Switchable conductivity properties of 1 and 2 were realized by the crystal to mesophase structure transition. The conductivity of the mesophase for 1 and 2 is higher than the corresponding crystal phase. Furthermore, magnetic phase transition with the non-common hysteresis loop for 2 is observed being triggered by the structure and dielectric transition. To the best of our knowledge, this study might be the rare multi-functional switchable examples with dielectric, conductivity, and magnetic transition.

Mechanoresponsive Spin via Spin-Lattice Coupling in Organic Cocrystals.

The response of crystal structure to external stimuli provides potential applications in the areas of detection, diagnosis, and repair. In this work, we fabricate two allotropic organic cocrystals, with different space groups and lattice parameters, with identical donor and acceptor molecules inside them. Under external stimuli, lattice vibration and electron-phonon coupling present pronounced differences in these two types of crystals, where different strengths of spin polarizations are observed. Furthermore, due to pronounced differences in coupling between lattice and spin inside the allotropic charge transfer crystals, the magnetic field presents a discrepant tunability on both transmission and fluorescence lifetimes. Through decreasing temperature or applying external electric field, the electron-phonon coupling coefficient presents a decreasing tendency, which will affect the dipole and dielectric constant in the allotropic crystals differently.

Temperature-induced neutral-to-ionic phase transition of the charge-transfer crystal tetrathiafulvalene-fluoranil

The Temperature Induced Neutral to Ionic phase Transition (TI-NIT) is a rare phenomenon occurring in mixed stack charge transfer (CT) crystals made up of alternating $\pi$-electron Donor (D) and Acceptor (A) molecules. We were able to grow crystals of Tetrathiafulvalene-Fluoranil (TTF-FA), and to show that it undergoes TI-NIT like the prototype CT crystal TTF-Chloranil. We characterized both room and low T phases through IR and Raman spectroscopy and XRD, demonstrating that while TTF-FA is quasi-neutral at room T, its ionicity jumps from 0.15 to 0.7 at low T, therefore crossing the Neutral-Ionic borderline. The transition, occuring around 150K, is first order, with large thermal hysteresis and accompanied by crystal cracking. In the high T phase D and A molecules lie on inversion center, i.e. the stacks are regular, whereas the low T phase is characterized by the loss of the inversion symmetry along the stack as the stacks are strongly dimerized and by the doubling of the unit cell.

Spin Multiplicity and Solid-State Electrochemical Behavior in Charge-Transfer Co-crystals of DBTTF/F4TCNQ

Charge-transfer crystals exhibit unique electronic and magnetic properties with interesting applications. The charge-transfer single crystal formed by dibenzotetrathiafulvalene (DBTTF) together with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) presents a long-range ordered supramolecular structure of segregated stacks, with a unitary degree of charge transfer. Thus, the crystal structure is composed of dimerized radical molecules with unpaired electrons. The energy levels and the spin degrees of freedom of this material were investigated by solid-state electrochemistry and electron paramagnetic resonance (EPR) spectroscopy. The electrochemical data, supported by density functional theory calculations, show how this organic Mott insulator has an electronic gap in the range of hundreds of meV. EPR experiments show the presence of a ground-state S = 1 triplet spin state along with localized S = 1/2 spins. The calculations also predict a ground-state triplet configuration, with the singlet configuration at 170 meV higher energy. DBTTF/F4TCNQ seems to be a candidate material for organic electronic and spintronic applications.

Relaxor ferroelectricity in the polar M2P-TCNQ charge-transfer crystal at the neutral-ionic interface

We investigated the mixed-stack charge-transfer crystal, N,N'-dimethylphenazine-TCNQ (M$_2$P-TCNQ), which is polar at room temperature and just at the neutral-to-ionic interface (ionicity $\rho \approx 0.5$). We detect the typical dielectric signature of a relaxor ferroelectric and an asymmetric positive-up-negative-down behavior. While relaxor ferroelectricity is usually ascribed to disorder in the crystal, we find no evidence for structural disorder in the investigated crystals. To elucidate the origin of M$_2$P-TCNQ's dielectric properties we perform parallel structural and spectroscopic measurements, associated with theoretical modeling and quantum-mechanical calculations. Our combined effort points to a highly polarizable electronic system that is strongly coupled to lattice vibrations. The found indications for polarization reversal imply flipping of the bent conformation of the M$_2$P molecule with an associated energy barrier of a few tens of an eV, broadly consistent with an Arrhenius fit of the dielectric relaxation times. While the polarization is mostly of electronic origin, its possible reversal implies slow collective motions that are affected by solid-state intermolecular interactions.

Isostructural Charge-Transfer Cocrystals Based on Triptycene End-Capped Quinoxalinophenanthrophenazine

Charge transfer (CT) crystals of an electron donor and an acceptor have electronic properties that are different from the two pure components. Despite the great potential of such CT crystals have f...

Guest-Binding-Induced Interhetero Hosts Charge Transfer Crystallization: Selective Coloration of Commonly Used Organic Solvents.

Unprecedented interheteromacrocyclic hosts charge transfer (CT) crystals were generated by cooling organic solutions containing p-dimethoxybenzene-constituted pillar[5]arene (P5A) and p-benzoquinone-constituted pillar[5]quinone (P5Q). Despite the weak CT interaction known between p-dimethoxybenzene and p-benzoquinone and the lack of formation of CT complexes between P5A and P5Q in the solution phase, CT cocrystals between P5A and P5Q were formed with solvent molecules included into the hosts' cavities. Such a cocrystallization arises from an elegant synergy between the CT interaction and solvent-binding-promoted crystallization. The interhetero hosts CT crystals were studied by optical and electron microscopic techniques, X-ray powder diffraction, solid-state NMR, UV-vis, IR spectroscopic studies, and X-ray single-crystal studies. The solvent complexation was critical for formation of the supramolecular CT microcrystals. The CT absorption bands faded upon removing the solvent molecules under vacuum, but they could be recovered by reuptake of the solvent molecules. Intriguingly, the CT absorption bands and uptake kinetics are distinguishably different for various organic solvents, thus providing a unique way to distinguish between different commonly used chemicals.

Charge-transfer crystal with segregated packing structure constructed with hexaarylbenzene and tetracyanoquinodimethane

Charge-transfer (CT) crystals bearing segregated domains between the hexaarylbenzene and TCNQ are a promising platform for developing new organic functional solid-state materials.

Antibacterial activity of In-doped ZnO nanoparticles

Undoped and In-doped zinc oxide (ZnO) nanoparticles have been synthetized by sol gel technique. The In doping concentration was ranged from 0 to 5 at.%. The prepared nanoparticles structural and morphological properties have been investigated by means of X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The photoluminescence (PL) spectroscopy was used to determine the electronic defects in the samples band gap. The antibacterial activities of the synthetized nanoparticles have been tested against Gram negative and positive bacteria’s referring to the inhibition zone radius measurement. The obtained results indicated that In dopant improves its antibacterial activity. The antibacterial activity improvement with In doping effect is attributed to the enhancement of electronic defects including vacancy defect Vzn and interstitial defect Zni with In doping. These defects behave as electrons and holes source necessary for reactive oxygen species (ROS) responsible for bacteria’s destruction. We noticed that the prepared ZnO nanoparticles exhibit a low antioxidant activity, this is attributed to the bonded hydrogen charge transfer crystal screening.

Unraveling the Origin of High-Efficiency Photoluminescence in Mixed-Stack Isostructural Crystals of Organic Charge-Transfer Complex: Fine-Tuning of Isometric Donor–Acceptor Pairs

Charge-transfer (CT) crystals show unique transport and emission properties which are substantially different from those of individual electron donor (D) and acceptor (A) molecules constituting the...

Ultrafast Tuning of Various Photochemical Pathways in Perylene–TCNQ Charge-Transfer Crystals

Excited-state dynamics in a strong charge-transfer (perylene)3–7,7,8,8-tetracyanoquinodimethane (P3T1) single-crystal system was studied by use of femtosecond transient absorption and upconversion ...

Recent Progress in the Development of Solid‐State Luminescent o‐Carboranes with Stimuli Responsivity

Abstracto‐Carborane, a cluster compound containing boron and adjacent carbon atoms, displays intriguing luminescent properties. Recently, compounds containing o‐carborane units were found to show suppressed aggregation‐induced quenching and intense solid‐state emission; they also show potential for the development of stimuli‐responsive luminochromic materials. In this Minireview, we introduce three kinds of fundamental photochemical properties: aggregation‐induced emission, twisted intramolecular charge transfer in crystals, and environment‐sensitive excimer formation in solids. Based on these properties, several types of luminochromism, such as thermos‐, vapo‐, and mechanochromism, have been discovered. Based mainly on results from recent studies, we illustrate these mechanisms as well as unique luminescent behaviors of o‐carborane derivatives.

Recent Progress in the Development of Solid-State Luminescent o-Carboranes with Stimuli Responsivity.

o-Carborane, a cluster compound containing boron and adjacent carbon atoms, displays intriguing luminescent properties. Recently, compounds containing o-carborane units were found to show suppressed aggregation-induced quenching and intense solid-state emission; they also show potential for the development of stimuli-responsive luminochromic materials. In this Minireview, we introduce three kinds of fundamental photochemical properties: aggregation-induced emission, twisted intramolecular charge transfer in crystals, and environment-sensitive excimer formation in solids. Based on these properties, several types of luminochromism, such as thermos-, vapo-, and mechanochromism, have been discovered. Based mainly on results from recent studies, we illustrate these mechanisms as well as unique luminescent behaviors of o-carborane derivatives.

(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

The 3:2 Charge Transfer (CT) co-crystal (Perylene)3(TCNQF1)2 is grown by the Physical Vapor Transport (PVT) method, and characterized structurally and spectroscopically. Infrared analysis of the charge sensitive modes reveals a low degree of charge transfer (less than 0.1) between donor and acceptor molecules. The crystal is isostructural to the other 3:2 CT crystals formed by Perylene with TCNQF2 and TCNQF4, whereas such stoichiometry and packing is not known for the CT crystals with non-fluorinated TCNQ. The analysis of the isostructural family of 3:2 Perylene–TCNQFx (x = 1,2,4) co-crystal put in evidence the role of weak F…HC bonding in stabilizing this type of structure