Charge-transfer Complexes Research Articles

Salicylic Acid-Modified Sm-TiO2 for Photoluminescence and Photocatalysis under Real Sunlight: Synergistic Effects between Ligand-to-Metal Charge Transfer (LMCT) and Sm3+ Dopant.

A salicylic-acid (SA)-modified samarium-doped TiO2 complex (Sm-TiO2/SA) was synthesized via a sol-gel method followed by impregnation. A Raman Fourier transform IR and X-ray photoelectron spectroscopic study showed that SA (as an electron donor) forms a surface complex on the Sm-TiO2 surface through its phenolic/carboxylic functional groups. In the Sm-TiO2/SA complex, a ligand-to-metal charge transfer (LMCT) is active, inducing a marked red-shift in the absorption spectrum of TiO2, which extends to 550-600 nm. The synergetic effect between the LMCT process and the luminescent properties of the lanthanide ions (Sm3+) is discussed and supported by the photoluminescence spectra. Further photocatalytic experiments (under sunlight) and the study of the effect of different scavengers show the presence of competitive reactions between de-ethylation and cleavage of Rhodamine B (RhB) during its degradation. With the Sm-TiO2/SA complexes, the superoxide radical ion (O2 •-) is the main active species responsible for the N-de-ethylation pathway under sunlight irradiation. The cleavage of RhB by the hydroxyl radical (•OH) appears, instead, to dominate with the Sm-TiO2 photocatalysts.

Contrasting Photosensitized Processes of Ru(II) Polypyridyl Structural Isomers Containing Linear and Hooked Intercalating Ligands Bound to Guanine-Rich DNA.

The DNA binding and cellular uptake of the lambda enantiomer of two bis-tetraazaphenanthrene (TAP) Ru(II) polypyridyl complexes containing either a linear dppn (1) or a hooked bdppz (2) benzodipyridophenazine ligand are reported, and the role of different charge-transfer states of the structural isomers in the photo-oxidation of guanine is explored. Both complexes possess characteristic metal-to-ligand charge-transfer (MLCT) bands between 400 and 500 nm and emission at ca. 630 nm in an aerated aqueous solution. Transient visible absorption (TrA) spectroscopy reveals that 400 nm excitation of 1 yields a dppn-based metal-to-ligand charge-transfer (MLCT) state, which in turn populates a dppn intraligand (3IL) state. In contrast, photoexcitation of 2 results in an MLCT state on the TAP ligand and not the intercalating bdppz ligand. Both 1 and 2 bind strongly to double-stranded guanine-rich DNA with a loss of emission. Combined TrA and time-resolved infrared (TRIR) spectroscopy confirms formation of the guanine radical cation when 2 is bound to the d(G5C5)2 duplex, which is not the case when 1 is bound to the same duplex and indicates a different mechanism of action in DNA. Utilizing the long-lived triplet excited lifetime, we show good uptake and localization of 2 in live cells as well as isolated chromosomes. The observed shortening of the excited-state lifetime of 2 when internalized in cell chromosomes is consistent with DNA binding and luminescent quenching due to guanine photo-oxidation.

Enter MnIV-NHC: A Dark Photooxidant with a Long-Lived Charge-Transfer Excited State.

Detailed photophysical investigation of a Mn(IV)-carbene complex has revealed that excitation into its lowest-energy absorption band (∼500 nm) results in the formation of an energetic ligand-to-metal charge-transfer (LMCT) state with a lifetime of 15 ns. To the best of our knowledge, this is the longest lifetime reported for charge-transfer states of first-row-based transition metal complexes in solution, barring those based on Cu, with a d10 configuration. A so-called superoxidant, Mn(IV)-carbene exhibits an excited state potential typically only harnessed via excited states of reactive organic radical species. Furthermore, the long-lived excited state in this case is found to be a dark doublet, with its transition to the quartet ground state being spin-forbidden, a contrast to most first-row literature examples, and a possible cause of the long lifetime. Showcasing excited state properties which in some cases exceed those of complexes based on precious metals, these findings not only advance the library of earth-abundant photosensitizers but also shed general insight into the photophysics of d3 and related Mn complexes.

Calculation of the formation enthalpies of charge-transfer complexes with iodine from the binding constants at 298.15 K

There is a continuing interest in charge-transfer complex chemistry, particularly in their formation thermodynamics. Nowadays, the binding constants and Gibbs energies of formation are available for many complexes. However, the experimental determination of the complexation enthalpies is a more difficult procedure, as it usually requires the establishment of the temperature dependence of the binding constant. Our recent studies of the compensation relationship in the thermodynamics of solvation in hydrogen-bonded systems opened the way to the calculation of the enthalpies of specific (i.e., localized donor-acceptor) interactions (Δint(sp)H) directly from the Gibbs energies at 298.15 K (Δint(sp)G). The calculation procedure is based on the following equation: Δint(sp)G/(kJ·mol−1) = 0.66·Δint(sp)H/(kJ·mol−1) + 2.5n (n corresponds to the coordination number of a solute).In the present work, we checked whether the above relation can be applied to the complex formation between halogens (primarily iodine) and organic electron donors. For 152 complexes with aromatics, nitrogen, oxygen, sulfur, selenium, and phosphor-containing compounds, the formation enthalpies were estimated using the data on equilibrium constants at 298.15 K. In most cases, agreement with the experimental binding enthalpies within the expected measurement error was observed (RMS = 1.4 kJ·mol−1, AD = –0.4 kJ·mol−1).

Amine-decorated metal-organic frameworks MIL-53(Al) on titanosilicate zeolite ETS-10 for radioactive iodine entrapment

The storage/disposal of the hazardous fission product iodine (I2) from waste of nuclear industries has caused worldwide concerns because of its severely negative impacts on organisms and environments. Therefore, searching for appropriate adsorbent is of great importance for effective capture of radioactive I2. Herein, a series of novel hierarchical adsorbents, composed of the nanoscale Materials of Institute Lavoisier-53(Al) (MIL-53(Al)) or its amine functionalized derivative NH2-MIL-51(Al) onto a supporter Engelhard Titanosilicate-10 (ETS-10) were successfully synthesized via a wet impregnation method. The performance for I2 removal of the absorbents (MIL-53(Al), NH2-MIL-51(Al) and NH2-MIL-51(Al)@ETS-10) were studied as functions of loading amount, morphology and pore structure, respectively. The NH2-MIL-51(Al)@ETS-10 represents the best adsorption performance due to its good cooperative effects including larger surface area, higher load capacity, strong affinity of charge-transfer complexes with I2 (-NH2 or –NH with I). The adsorption capacity of NH2-MIL-51(Al)@ETS-10 could be reached to 1.16 g·g−1 and is ∼ 2.5 and 5 times higher than the NH2-MIL-51(Al) and MIL-51(Al), respectively. The kinetics and isotherms for adsorption could be fitted via pseudo-second-order and Langmuir models, respectively, indicating the strong monolayer chemisorption interactions. The study manifests that the designed material has certain potential for application in I2 entrapment.

Effect of methyl trifluoride substitution on colorless transparency of polyimide: A DFT/TD-DFT study

The rapid advancement of flexible electronic devices has rendered high-performance colorless transparency polyimide (PI) films essential for energy storage and devices. However, there still remains controversy regarding the charge-transfer complexes in relation to the optical properties of PIs. Herein, we employed a combination of DFT and TD-DFT methods to elucidate the hole and electron characteristics of PIs. The results revealed that the incorporation of a CF3 group significantly enhances the dipole moment. Notably, the incorporation of CF3 groups onto both the anhydride and diamine units impedes charge transfer, resulting in a reduction of the HOMO energy level and an increse of the LUMO energy. The calculation results also indicate that the introduction of CF3 groups markedly hinders charge transfer within P4 in its excited state, leading to the minimum values for three characteristic parameters (D = 2.60 Å, CT = 0.51 e, t = 0.53 Å). Therefore, P4 exhibits a shortest charge transfer pathway resulting in minimal electron transfer and obvious blue-shifted UV–vis spectra, thus contributing to its excellent colorless transparency. This work provides a theoretical foundation and guidance for targeted design and development of colorless transparent PI films.

Regulating the redshift of the charge transfer band edge and antithermal quenching by ion substitution strategy in YP1-xVxO4:Eu3+ phosphor

The redshift of the charge transfer band (CTB) edge of phosphor induced by temperature rise is pervasively accompanied by antithermal quenching. Accordingly, exploring the mechanism of the CTB redshift is thus not only propitious for optimizing the sensitivity of optical thermometry but also tenders a new idea for the design of antithermal quenching phosphors. Herein, a family of YP1-xVxO4:Eu3+ phosphors were designed via the V5+/P5+ ion substitution strategy. With the increase of the V5+ ratio, the relative integral intensity of the 5D0→7F2 transition multiplies from 1.25 to 28.67 times under CTB edge excitation. Moreover, by Gaussian fitting, the reduction degree of vanadate band gap energy 1E (1T1)→1B2 (1T2), 1A2 (1T1)→1B2 (1T2) increased from 0.122 eV and 0.065 eV to0.162 eV and 0.083 eV, respectively, in the range of 303–523 K. Both reveal an enhance in redshift of the excitation spectra. The decrease of charge transfer state (CTS) energy level and the alteration of photoelectron thermal population are two mechanisms that induce CTB redshift. Specifically, the decrease of the CTS level is dominant in the YPO4:Eu3+ sample, and the thermal population of the higher vibrational levels of the VO43−ground state is dominant in the presence of a tiny amount of V5+ doping. In addition, according to the experimental phenomenon, a dual-mode temperature sensing scheme based on excitation intensity ratio (EIR) and single band ratiometric (SBR) is proposed. Y0.9P0.1V0.9O4:0.1Eu3+ achieves a maximum sensitivity of Sr-max = 4.040 % K−1 and a minimum temperature determination uncertainty of δT = 0.124 K at 323 K, which excellent performance indicates that this is a promising non-contact optical thermometer.

Design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks for highly sensitive detection of chlorpyrifos in real samples.

Chlorpyrifos (CPS) is widely found in food and water sources due to agricultural use, posing health and environmental risks. Therefore, this work introduces a fluorescent sensor design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks (UiO-66-NH2@AgNPs) for accurate examination of CPS. Briefly, UiO-66-NH2 was synthesized hydrothermally, exhibiting weak luminescence owed to ligand-to-metal charge transfer (LMCT). Here, it limits its direct utility in fluorescence-based detection. To address this limitation, silver nanoparticles (AgNPs) were introduced into UiO-66-NH2, enhancing fluorescence via the metal-enhanced fluorescence (MEF) effect. Briefly, a comprehensive spectral analysis such as XPS, SEM, TEM, PXRD, etc., was performed to validate the synthesis of UiO-66-NH2@AgNPs. Subsequent evaluation revealed that CPS effectively quenched the luminescence intensity of UiO-66-NH2@AgNPs through a static quenching mechanism. The fluorescence intensity exhibited good linearity with CPS concentration in the span of 10 to 1,000 ng/mL, with a recognition limit of 191.5ng/mL(S/N = 3). The interaction involved Ag-S bond formation and electrostatic interactions, reducing fluorescence intensity. The method was confirmed through successful CPS detection in fruit samples. The UiO-66-NH2@AgNPs nanoprobe offers a simple, sensitive, and accurate platform for CPS sensing, with potential for future use in detecting CPS in fruits and vegetables.

Functional group-specific reduction of Cr(VI) by low molecular weight organic acids in frozen solution: Kinetics, mechanism and DFT calculation

Low molecular weight organic acids (LMWOA) are commonly present in natural water and play a pivotal role in the reduction of Cr(VI). In frozen solutions, the efficiency of Cr(VI) reduction is significantly enhanced due to the freezing concentration effect. However, this facilitation is found to be contingent upon the functional groups of LMWOA in this study. To be specific, LMWOA and Cr(VI) can form five-membered ring complexes, which greatly enhance electron transfer efficiency through Ligand-to-Metal Charge Transfer (LMCT). DFT calculations indicate that oxygen-containing groups located on carbon atoms at α positions play a crucial role in forming these complexes, ultimately determining the kinetics of Cr(VI) reduction. Moreover, freezing not only increases proton concentrations but also reduces free water molecule content in the liquid-like layer (LLL), thereby affecting LMWOA species through regulation of protonation and hydrolysis, and subsequently impacting reaction mechanisms. The stoichiometric ratios between LMWOA and Cr(VI) exceed theoretical values due to complexation with Cr(III). The reduction of Cr(VI) by LMWOA in frozen solutions is inhibited by soil solution, while the degree of inhibition varies among different types of LMWOA.

Organocatalyzed iodine-mediated reversible-deactivation radical polymerization via photoinduced charge transfer complex catalysis

Organocatalyzed iodine-mediated reversible-deactivation radical polymerization via photoinduced charge transfer complex catalysis

Nano-catalytic behavior of CeO2 nanoparticles in dye adsorption: Synthesis through bio-combustion and assessment of UV-light-driven photo-adsorption of indigo carmine dye

This study explores the adsorption of indigo carmine dye using bio-combusted cerium oxide nanoparticles (CeO2 NPs). CeO2 NPs were synthesized using a bio-combustion method, and then subjected to structural, morphological, and optical characterization for thorough investigation. Structural investigation was carried out using X-ray diffraction (XRD), which revealed a cubic structure with evaluated average crystallite size of 11.55 nm. Later, the same was verified by employing W–H plot (13.57 nm). UV–Vis spectroscopy revealed an effective band gap of 3 eV suited for photocatalytic applications. The metal-oxygen phonon band at 986.32 cm−1 and 871.96 cm−1 is confirmed using Infrared Spectroscopy (FTIR). The morphological analysis was done using Transmission and Scanning Electron Microscopy (TEM and SEM), which revealed well-dispersed, aggregated structure enclosing spherical nanoparticles with an average size of ∼14 nm. The early precursors were validated using EDAX analysis and SEM. Optical characteristics were investigated using photoluminescence (PL), which revealed a large charge transfer band between 360 nm and 435 nm. The dye removal efficiency of CeO2 NPs was evaluated against Indigo Carmine dye using UV light. The results showed that the significantly adsorption, with more than 70 % removed after 150 min. Kinetic experiments revealed that the depreciation occurred via a pseudo-first-order reaction process. Furthermore, the impacts of certain factors such as dye dosage, pH, reusability, and scavenger on adsorption rate were explored and shown to be effective values for the adsorption process. This study emphasizes the potential of CeO2 NPs as excellent photocatalysts for environmental remediation, especially in dye removal applications.

Synthesis, optical properties, and applications of Eu3+, Na+-doped high-color-purity Sr3MgNb2O9 red phosphors for w-LEDs and the detection of latent fingerprints

A series of novel phosphors, doping Eu3+ and Na+ ions in the Sr3MgNb2O9 (SMNO) crystal lattice (SMNO:xEu3+, xNa+, x = 0.5–30 mol%), was successfully synthesized through high-temperature solid-state reaction. X-ray diffraction (XRD) analysis and Rietveld refinement confirmed the successful synthesis of SMNO:Eu3+, Na+. The phosphor belongs to the hexagonal crystal system and the P3¯m1 (No.164) space group. The bandgap energy of SMNO was calculated with Materials Studio and measured with the use of diffuse reflectance spectroscopy. The excitation spectrum of SMNO:Eu3+, Na+ displays multiple narrow absorption peaks in the violet-blue region as well as a charge transfer band (CTB) near 300 nm, exhibiting the highest peak at 394 nm. Four distinct characteristic peaks are observed in the emission spectrum of SMNO:Eu3+, Na+. Notably, the peak at 601 nm shows the highest emission intensity due to the radiative transition from 5D0→7F2. By varying doping concentrations, it was determined that an optimal concentration of 5 mol%Eu3+ resulted in phosphors, with high color purity exceeding 99 %. Concentration quenching is attributed to the nearest neighbor ions interaction. Furthermore, SMNO:Eu3+, Na+ exhibited good stability in 300–480 K, with luminescent intensity remaining 68.6 % at 420 K and 54.4 % at 480 K compared to room temperature (300 K). The internal quantum efficiency (IQE) of SMNO:5%Eu3+, 5 %Na+ is 65.0 %. Both red and white light-emitting diodes (LEDs) were prepared using SMNO:Eu3+, Na+. The chromaticity coordinates of w-LED were measured as (0.357, 0.376), correlating to a correlated color temperature (CCT) of 4685 K and exhibiting a good color rendering index (CRI, Ra = 88). Additionally, the latent fingerprint (LFP) development demonstrated clear visualization of Levels I-III characteristic structures of fingerprints when utilizing SMNO:Eu3+, Na+. These findings suggest promising applications for SMNO:Eu3+, Na+ in w-LED lighting and LFP development.

Regulation of Dihedral Angle on Molecular Engineering for Enhancing Triboelectric Performance

AbstractThe performance of triboelectric polymers relies on their molecular structure. Therefore, investigating how to construct high‐performance molecular structures of triboelectric polymers becomes imperative, yet the relationship between microscopic structural parameters and triboelectric performance remains unclear. In this study, the relationship is studied between dihedral angles of adjacent conjugated planes and triboelectric performance. Various polyimide monomers are synthesized to manipulate the conjugated dihedral angles within the molecular chains. Introducing larger dihedral angles in polyimides (PIs) reduces the conjugation between molecular chains, suppressing the formation of charge transfer complexes (CTCs), and widening the energy gap between molecular orbitals. With the increase in dihedral angles, the output performance improved by 100%. The surface charge density of 335 µC·m−2 is achieved through the synergistic effect of the high charge retention capability of the PI film and the high triboelectric properties of the corona‐polarized fluorinated ethylene propylene (FEP). A large dihedral angle can form numerous deep traps and effectively prevent charge escaping while ensuring stable output. This study provides a feasible strategy for investigating the construction of high triboelectric performance molecular structures, enriching the understanding of how molecular structures influence the triboelectric properties of polymer materials and promote high‐performance fluorine‐free and environmentally friendly polymers.

Closo-B10H8-10-PhI-1-COOH]- Anion: An Intermediate for Functional Anionic Carboxylate Ligands.

A potentially general intermediate, [closo-B10H8-10-PhI-1-COOH]-, for a class of functional anionic carboxylic acids, [closo-B10H8-10-X-1-COOH]2-, was obtained in four steps and 26% overall yield from [closo-B10H10]2-. It was converted to the pyridinium derivative (X = C5H5N+) and subsequently to coordination complexes with (phen)2Cu2+ and (phen)2Zn2+ ions. Both the acid and Zn(II) complex exhibit a cage-to-pyridine charge-transfer band. The availability of such acids opens access to functional metal-ion complexes with compensated charges.

Preparation, structure and optical properties of TCNB-based charge-transfer cocrystals

Organic charge transfer cocrystals exhibit interesting properties due to their multi-components synergistic and collective effect. Herein, using 1,2,4,5-tetracyanobenzene (TCNB) as electron acceptor, carbazole (CARB), dibenzothiophene (DBZP) and dibenzofuran (DBZF) as electron donors, three charge transfer cocrystals of CARB-TCNB, DBZP-TCNB and DBZF-TCNB were synthesized by solvent evaporation method and solvent-assisted grinding method. These cocrystals were constructed based on the π–π stacking interactions and CH…N hydrogen bonds and confirmed by the SXRD analysis. The stacking modes are consistent with the model that predicted by molecular electrostatic potential analysis (ESP). The IGM and AIM analyses suggested that the π-π stacking and CH…N hydrogen bonds are weak in nature. The purity and homogeneity of cocrystals and grinding products were verified by PXRD analysis. In addition, the IR, UV–vis absorption and luminescent properties were investigated, and the cocrystals and grinding products exhibited different behaviors from that of their precures. In short, this work not only reports the CT complexes synthesized by liquid- and solid- strategies, but also provides an in-depth understanding of the spectral changes caused by the CT interactions.

Achieved High-Sensitivity Single-Band Ratiometric Optical Thermometry by Manipulating the Intervalence Charge-Transfer Band Position.

Currently, optical thermometry has received widespread attention because of its noncontact and wide temperature range, but most of them are based on the application of dual-band optical ratiometric thermometry, so the development of a single-band ratiometric (SBR) optical thermometry, which is easier to analyze and use, is particularly important. In this work, the position of the intervalence charge-transfer (IVCT) band for Na2Gd2-xLaxTi3O10:Pr3+ (x = 0, 0.5, 1.0, 1.5, 2.0) was modulated using Gd/La substitution, enhancing the thermal response difference of Pr3+ 1D2 → 3H4 under charge-transfer band (CTB) and IVCT band excitation, thereby achieving high-sensitivity SBR optical thermometry, and the maximum relative sensitivity (Sr-max) reached 2.95% (at 298 K). In addition, this series of phosphors has high-color-purity red emission, indicating that it has potential for multifield applications.

Effects of Structural Constraints on Excited-State Properties in Dimeric Cu(I) Diimine Complexes.

Copper(I) bis-diimine complexes have played important roles in light-activated processes that can lead to their potential applications in photocatalysis and chemical sensing. Their metal-to-ligand charge-transfer (MLCT) excited-state properties are tunable by various structural factors. Dimeric Cu(I) complexes with connecting diimine derivative ligands offer another structural tuning platform for the excited-state properties. Here, we investigate excited-state properties in two covalently connected dimeric Cu(I)'s with varying structural constraints exerted by the number of carbons in the polyethylene bridge (C0 and C4) connecting the two copper(I) diimine moieties. An interesting feature of Cu(I) diimine complexes is their ability to flatten following a photoinduced structural change. Herein, we observe larger structural constraints and more structural rearrangement required upon excitation of the longer bridged complex C4 to achieve a conformation toward a more flattened tetrahedral coordination geometry compared to the shorter bridged C0. Vibrational wavepacket analysis of these complexes further supports the effect of these structural constraints where we observe a more rapid dephasing of the C0 complex, as opposed to the C4 complex, despite similar normal mode vibrations. The experimental results were supplemented by TDDFT calculations. The studies provide insight into using metal-metal interactions through constraints to tune excited-state dynamics and pathways.

Electronic and Molecular Structures of a Series of Nickel Bis-1,1-Dithiolates.

A series of homoleptic Ni bis-1,1-dithiolates, [Ni(S2C2RR')2]2- (R=CN, R'=CN, CO2Et, CONH2, Ph, Ph-4-Cl, Ph-4-OMe, Ph-4-NO2, Ph-3-CF3, Ph-4-CF3, Ph-4-CN; R=NO2, R'=H; R=R'=CO2Et) have been synthesized from the reaction of the alkali metal salt of the ligand and nickel chloride, and isolated as tetraphenylphosphonium or tetrabutylammonium salts. The complexes were characterized by X-ray crystallography, high-resolution mass spectrometry, and infrared (IR), nuclear magnetic resonance (NMR) and electronic absorption spectroscopies. The molecular structures show a rigidly square planar Ni(II) center linking two four-membered chelate rings whose dimensions are constant across the series. The electronic effect of the ligand substituent is revealed in the 13C NMR and electronic spectra, and corroborated by density functional calculations. Electron withdrawing groups deshield the low-field CS2 resonance, and the signature charge transfer band in the visible region is red-shifted. These observables have been accurately reproduced computationally, and revealed the Ni contribution to the ground state diminishes with decreasing electron withdrawing capacity of the ligand substituent. In contrast to 1,2-dithiolates, the redox inactivity afforded by 1,1-dithiolates stems from the smaller chelate ring and substantially reduced sulfur content that is key to stabilizing the radical form.

Charge-Transfer Complexes: Fundamentals and Advances in Catalysis, Sensing, and Optoelectronic Applications.

Supramolecular assemblies, formed through electronic charge transfer between two or more entities, represent a rich class of compounds dubbed as charge-transfer complexes (CTCs). Their distinctive formation pathway, rooted in charge-transfer processes at the interface of CTC-forming components, results in the delocalization of electronic charge along molecular stacks, rendering CTCs intrinsic molecular conductors. Since the discovery of CTCs, intensive research has explored their unique properties including magnetism, conductivity, and superconductivity. Their more recently recognized semiconducting functionality has inspired recent developments in applications requiring organic semiconductors. In this context, CTCs offer a tuneable energy gap, unique charge-transport properties, tailorable physicochemical interactions, photoresponsiveness, and the potential for scalable manufacturing. Here, an updated viewpoint on CTCs is provided, presenting them as emerging organic semiconductors. To this end, their electronic and chemical properties alongside their synthesis methods are reviewed. The unique properties of CTCs that benefit various related applications in the realms of organic optoelectronics, catalysts, and gas sensors are discussed. Insights for future developments and existing limitations are described.

Cooperative Binding and Chirogenesis in an Expanded Perylene Bisimide Cyclophane.

The encapsulation of more than one guest molecule into a synthetic cavity is a highly desirable yet a highly challenging task to achieve for neutral supramolecular hosts in organic media. Herein, we report a neutral perylene bisimide cyclophane, which has a tailored chiral cavity with an interchromophoric distance of 11.2 Å, capable of binding two aromatic guests in a π-stacked fashion. Detailed host-guest binding studies with a series of aromatic guests revealed that the encapsulation of the second guest in this cyclophane is notably more favored than the first one. Accordingly, for the encapsulation of the coronene dimer, a cooperativity factor (α) as high as 485 was observed, which is remarkably high for neutral host-guest systems. Furthermore, a successful chirality transfer, from the chiral host to encapsulated coronenes, resulted in a chiral charge-transfer (CT) complex and the rare observation of circularly polarized emission originating from the CT state for a noncovalent donor-acceptor assembly in solution. The involvement of the CT state also afforded an enhancement in the luminescence dissymmetry factor (glum) value due to its relatively large magnetic transition dipole moment. The 1:2 binding pattern and chirality-transfer were unambiguously verified by single-crystal X-ray diffraction analysis of the host-guest superstructures.