Circularly Polarized Luminescence Signals Research Articles

Double Heterohelicenes Composed of Benzo[b]- and Dibenzo[b,i]phenoxazine: A Comprehensive Comparison of Their Electronic and Chiroptical Properties.

Heterohelicenes are potential materials in molecular electronics and optics because of their inherent chirality and various electronic properties originating from the introduced heteroatoms. In this work, we comprehensively investigated two kinds of double NO-hetero[5]helicenes composed of 12H-benzo[b]phenoxazine (BPO) and 13H-dibenzo[b,i]phenoxazine (DBPO). These helicenes exhibit good electron-donor properties reflecting the electron-rich character of their monomers and were demonstrated to work as p-type semiconductors. The enantiomers of these helicenes show the largest class of dissymmetry factors for circularly polarized luminescence (CPL) (|gCPL| > 10-2) among helicenes reported to date. Interestingly, the signs of CPL are opposite for BPO and DBPO double helicenes of the same helicity. The origin of the large gCPL values and the inversion of the CPL sign was addressed by analysis of the transition electronic dipole moments and transition magnetic dipole moments based on TD-DFT calculations.

Amplified circularly polarized luminescence promoted by hierarchical self-assembly involving Pt···Pt interactions

The design and construction of highly effective circularly polarized luminescence (CPL)-active materials has aroused considerable attention due to their widespread applications in sensors, optical devices, and asymmetric synthesis. However, the exploration of novel CPL-active materials with high luminescence dissymmetry factor (glum) values is still a challenge. Herein, we describe a new approach for the preparation of supramolecular metallacycles with amplified CPL promoted by hierarchical self-assembly involving Pt···Pt interactions. Notably, the resultant metallacycles exhibited strong CPL signals with high glum values, while their corresponding precursors were CPL silent. The CPL amplification mechanism was comprehensively validated by ultraviolet-visible absorption, emission spectroscopy, nuclear magnetic resonance spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, coarse-grained molecular dynamics simulations, and time-dependent density functional theory calculations. This work thus provides the first example of preparing highly effective CPL-active materials based on hierarchical self-assembly involving Pt···Pt interactions.

Iodization-enhanced fluorescence and circularly polarized luminescence for dual-readout probe design

Circularly polarized luminescence (CPL) is a preferential emission from chiral systems. Introducing CPL to traditional small fluorescence probes will greatly enhance selectivity and sensitivity due to avoiding the background fluorescence. Small-molecule probes are practically useful for bioimaging and sensing but always suffer from weak CPL properties. To optimize chiral perturbation, the study of structure-CPL correlation is an urgent necessity. Here, we investigated the influence of 3, 3′-substituent of BINOL on optical properties and found that iodization could significantly enhance the fluorescence quantum yield (ΦF) and dissymmetry factor (|glum|). Based on this finding, we presented a strategy to design dual-readout probes emiting both robust total fluorescence and CPL upon activation. As an application example, we first designed a pair of thiols probes, R/S-P1, with the fluorescence readout showing good linear response to cysteine, and CPL signal displaying significant enhancement with |glum| from undetectable value to 0.7 × 10−3.

Self-Assembly and Circularly Polarized Luminescence from Achiral Pyrene-Adamantane Conjugates by Selective Inclusion with Cyclodextrins.

The interaction between guest chromophores or lumiphores with host chiral cavity and their induced chirality is an important topic in supramolecular chemistry. Kodaka and Harata proposed a rule to explain the induced circular dichroism of the guest chromophores by host cyclodextrins. However, it remains unknown how a circularly polarized luminescence (CPL) signal will change when the lumiphores interacted with cyclodextrins in different modes. Here, we designed an achiral pyrene-adamantane conjugated guest molecule, N-(pyren-1-yl)adamantane-1-carboxamide (ACNP), and investigated its interactions with α/β/γ-cyclodextrins (CDs) and its induced CPL. Depending on the size match of the pyrene, adamantine with different cyclodextrins, distinct performance was observed. While α-CD could not induce a CPL signal of ACNP, β-CD could induce CPL in two modes, through adamantyl or direct pyrenyl induction, which could produce a CPL signal with opposite signs. γ-CD could always induce a negative CPL signal. Therefore, a rule of induced CPL of lumiphores by cyclodextrins can be proposed.

Optically Active CdSe/CdS Nanoplatelets Exhibiting Both Circular Dichroism and Circularly Polarized Luminescence

AbstractLigand‐induced chirality in colloidal semiconductor nanocrystals attracts attention because of their tunable chiroptical properties. Here, the induced chirality and circularly polarized luminescence (CPL) are investigated as a function of the CdS shell growth in a range of 2D CdSe/CdS nanoplatelets (NPLs) capped with chiral ligands. Five samples of CdSe/CdS NPLs are synthesized by a one‐pot approach to vary the island‐like shell on a four‐monolayer (4 ML) CdSe NPLs core, which effectively reduces the interfacial strain energy. The successful preparation of L‐/D‐Cysteine‐capped CdSe/CdS NPLs with both tunable circular dichroism (CD) and CPL behaviors and a maximum anisotropic luminance factor (glum) of 5.29 × 10−4 is described. The induced chiroptical response shows a direct relationship with the formation of island‐like shell in the first and second stages and shows a clear signal evolution. In the third stage with a full coating shell, the CD and CPL signals are inversely proportional to the CdS shell thickness. The island‐like shell gives birth to the CPL signal, while the formation of full coating shell decreases the induced chirality. Such chiral and emissive NPLs provide an ideal platform for the rational design of semiconductor nanocrystals with chiroptical properties in areas of biomedicine, polarizers, and new generation of display devices.

Full‐Color and White Circularly Polarized Luminescence Promoted by Liquid Crystal Self‐Assembly Containing Chiral Naphthalimide Dyes

AbstractChiral emissive nematic liquid crystals (N*‐LCs) can greatly amplify the circularly polarized luminescence (CPL) signals promoted by a highly regular spiral self‐assembly in the LCs system. Naphthalimide (NI) derivatives have been assigned to be one of the most excellent chromophores for fluorescent materials. In this paper, a novel strategy is first developed to regulate full‐color CPL behavior of N*‐LCs through different chiral NI‐based dyes. Chiral NI‐based dyes are doped into nematic liquid crystals (E7, N‐LCs) to form N*‐LCs as CPL‐active liquid crystal materials. Most interestingly, this kind of N*‐LCs could emit standard white CPL signals (CIE coordinates: (0.31, 0.33)) by choosing the blue‐red match of two chiral NI‐based dyes at the appropriate ratio.

Spontaneous chiral self-assembly of CdSe@CdS nanorods

Spontaneous chiral self-assembly of CdSe@CdS nanorods

Propeller Configuration Flipping of the Trivalent Boron-Inducing Substituent Dependence of the Circularly Polarized Luminescence Sign in Triarylborane-Based [7]Helicenes.

We here disclose two triarylborane-based [7]helicenes, which contain a dimesitylboryl or a 2-(dimesitylboryl)phenyl at position 9 of the [7]helicene skeleton. The change in the peripheral substituent from dimesitylboryl to 2-(dimesitylboryl)phenyl induced doubling of |glum| and sign inversion of the circularly polarized luminescence (CPL). The substituent dependence of the CPL sign is reasonably explained by the propeller configuration flipping of boron, which has a significant influence on the chiroptical properties.

Self-Assembly of Peptide Hierarchical Helical Arrays with Sequence-Encoded Circularly Polarized Luminescence.

Self-assembled peptide materials with sequence-encoded properties have attracted great interest. Despite their intrinsic chirality, the generation of circularly polarized luminescence (CPL) based on the self-assembly of simple peptides has been rarely reported. Here, we report the self-assembly of peptides into hierarchical helical arrays (HHAs) with controlled supramolecular handedness. The HHAs can emit full-color CPL signals after the incorporation of various achiral fluorescent molecules, and the glum value is 40 times higher than that of the CPL signal from the solutions. By simply changing the amino acid sequence of the peptides, CPL signals with opposite handedness can be generated within the HHAs. The peptide HHAs can provide hydrophobic pockets to accommodate the fluorescent molecules with helical arrangement through strong aromatic stacking interactions, which are responsible for the CPL signals. This work provides a pathway to construct highly ordered chiral materials, which have broad applications in the chiroptical field.

Deep Blue Circularly Polarized Luminescence Response Behavior of an Achiral Pyrene-Based Emitter Regulated by Chiral Co-assembly Helical Nanofibers.

Supramolecular co-assembly provides a brand-new powerful strategy for regulating simple organic molecules into various hierarchical nano- and microstructures as smart functional materials. In particular, chiral supramolecular assemblies with strong fluorescent emission have received extensive attention for their application as circularly polarized luminescence (CPL) emitters. Herein, we synthesized three achiral pyrene derivatives, but only the chiral co-assembly (R/S-NMe2-Py-2) can exhibit the regular and orderly helical nanofiber via π-π stacking interaction between chiral N,N'-dimethyl-binaphthyldiamine enantiomers (R/S-NMe2) and the achiral pyrene derivative (Py-2). Interestingly, this kind of 2:1 molar ratio (R/S-NMe2)2-Py-2 co-assembly with a helical nanofiber structure can emit a strong deep blue CPL signal from the achiral pyrene-based emitter, and the dissymmetry factor gem value can reach 0.027 (λem = 423 nm) in the film from spin-coating.

Light‐Responsive Circularly Polarized Luminescence Polymers with INHIBIT Logic Function

AbstractDynamically tuning the emission of circularly polarized luminescence (CPL) materials through external stimuli is fascinating because of their fundamental and application interests. In this work, light‐responsive and luminescence‐tunable CPL‐active materials are synthesized by mixing achiral helical polymer containing vibration‐induced emission (VIE) molecules and spiropyran (SP) with a chiral helical polymer. Through regulating the distinct emission of VIE molecules and the reversible photoisomerization of SP, the dynamic Förster resonance energy transfer (FRET) can be explored to reversibly control the emission color of CPL in different states after light‐controlled isomerization. This project is the first comprehensive investigation of CPL‐active materials with VIE properties. Finally, taking the advantage of the multistimuli responsive CPL signal in different states, an “INHIBIT” logic gate with CPL signal output based on the combination of control of UV/vis light irradiation time and state alternation is constructed.

Handed Mirror Symmetry Breaking at the Photo-Excited State of π-Conjugated Rotamers in Solutions

The quest to decode the evolution of homochirality of life on earth has stimulated research at the molecular level. In this study, handed mirror symmetry breaking, and molecular parity violation hypotheses of systematically designed π-conjugated rotamers possessing anthracene and bianthracene core were evinced via circularly polarized luminescence (CPL) and circular dichroism (CD). The CPL signals were found to exhibit a (−)-sign, and a handed dissymmetry ratio, which increased with viscosity of achiral solvents depending on the rotation barrier of rotamers. The time-resolved photoluminescence spectroscopy and quantum efficiency measurement of these luminophores in selected solvents reinforced the hypothesis of a viscosity-induced consistent increase of the (−)-sign handed CPL signals.

Turn‐On Circularly Polarized Luminescence in Metal–Organic Frameworks

AbstractThe fabrication of circularly polarized luminescence (CPL) active materials by self‐assembly is still in its challenge. In this work, a family of homochiral metal–organic frameworks (MOFs) and metal–organic cages (MOCs) are constructed by solvothermal subcomponent self‐assembly. These MOFs feature an eta topology with trifold helical chains, while the MOCs adopt a cubic cage structure. The chiral ligands show two distinct types of conformations: “opened” and “closed” in MOFs and MOCs, respectively. Although homochiral MOFs and MOCs show similar spectra of circular dichroism and photoluminescence with similar quantum yields and lifetimes, the MOFs yield clear CPL signals and the CPL of MOCs are silent. The turn‐on CPL in MOFs achieved by tuning the conformation of ligands and controlling self‐assembly provides a new approach for development of CPL‐active MOF materials.

Adaptive Chirality of an Achiral Cage: Chirality Transfer, Induction, and Circularly Polarized Luminescence through Aqueous Host–Guest Complexation

Chirality transfer, induction, and circularly polarized luminescence (CPL) using supramolecular hosts, such as macrocycles and cages, have been explored for wide-ranging applications in chiral reco...

Circularly polarized lanthanide luminescence for advanced security inks.

Authenticating products and documents with security inks is vital to global commerce, security and health. Lanthanide complexes are widely used in luminescent security inks owing to their unique and robust photophysical properties. Lanthanide complexes can also be engineered to undergo circularly polarized luminescence (CPL), which encodes chiral molecular fingerprints in luminescence spectra that cannot be decoded by conventional optical measurements. However, chiral CPL signals have not yet been exploited as an extra security layer in advanced security inks. This Review introduces CPL and related concepts that are necessary to appreciate the challenges and potential of lanthanide-based, CPL-active security inks. We describe recent advances in CPL analysis and read-out technologies that have expedited CPL-active security ink applications. Further, we provide a systematic meta-analysis of strongly CPL-active Euiii, Tbiii, Smiii, Ybiii, Cmiii, Dyiii and Criii complexes, discussing the suitability of their photophysical properties and highlighting promising candidates. We conclude by providing key recommendations for the development and advancement of the field.

Strong-Induced CPL Emission Promoted from Achiral Conjugated Polymer-Containing Emissive Nematic Liquid Crystals (P-N*-LCs).

With the rapid development on 3D printing technology, more and more works have been devoted to 3D display. 3D display will really come true by using circularly polarized luminescence (CPL)-active materials with both high quantum yield and dissymmetry factor (gem ) in organic light-emitting diode or liquid crystals (LCs). But so far most of these CPL materials cannot meet the real application requirement because of the low gem values in the range of 10-5 -10-2 . In this paper, ternary chiral emissive LCs (P-N*-LCs) is designed by doping chiral binaphthyl-based enantiomers as chiral dopant (Guest 1) and achiral conjugated polymer as induced CPL emitter (Guest 2) into nematic liquid crystal (N-LCs) Host 5CB. Both Guest 1 and Guest 2 show excellent compatibility with Host 5CB. The obtained ternary P-N*-LCs can emit strong-induced CPL signal with gem up to 1.12 and ФFL up to 66.1%. This work first develops a new strategy for the smart design of excellent CPL materials from versatile achiral conjugation fluorescence polymers.

Sign inversion of excimer circularly polarized luminescence in water-soluble bipyrenyl oligopeptides through an odd-even effect

We prepared eight novel chiral arginine-bipyrenyl oligopeptides with different intramolecular distances between two organic luminophore fluorescent pyrene units and investigated their chiroptical properties in water at ambient temperature. These luminophores are highly soluble in water because of the presence of two arginine units; because they carry two pyrene units, they emit strong excimer circularly polarized luminescence (CPL) in the range of 450–600 nm (|gCPL| ≈ (0.1–0.5) × 10–2). When the number of atoms between the two intramolecular pyrenes units was even, the sign of the CPL signals was negative (−), whereas when the atom number was odd, the sign of the CPL signals was positive (+), even in water.

Chirogenesis and Pfeiffer Effect in Optically Inactive EuIII and TbIII Tris(β-diketonate) Upon Intermolecular Chirality Transfer From Poly- and Monosaccharide Alkyl Esters and α-Pinene: Emerging Circularly Polarized Luminescence (CPL) and Circular Dichroism (CD).

We report emerging circularly polarized luminescence (CPL) at 4f-4f transitions when lanthanide (EuIII and TbIII) tris(β-diketonate) embedded to cellulose triacetate (CTA), cellulose acetate butyrate (CABu), D-/L-glucose pentamethyl esters (D-/L-Glu), and D-/L-arabinose tetramethyl esters (D-/L-Ara) are in film states. Herein, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (fod) and 2,2,6,6-tetramethyl-3,5-heptanedione (dpm) were chosen as the β-diketonates. The glum value of Eu(fod)3 in CABu are +0.0671 at 593 nm (5F1) and −0.0059 at 613 nm (5F2), respectively, while those in CTA are +0.0463 and −0.0040 at these transitions, respectively. The glum value of Tb(fod)3 in CABu are −0.0029 at 490 nm (5F6), +0.0078 at 540 nm (5F5), and −0.0018 at 552 nm (5F5), respectively, while those in CTA are −0.0053, +0.0037, and −0.0059 at these transitions, respectively. D-/L-Glu and D-/L-Ara induced weaker glum values at 4f-4f transitions of Eu(fod)3, Tb(fod)3, and Tb(dpm)3. For comparison, Tb(dpm)3 in α-pinene showed clear CPL characteristics, though Eu(dpm)3 did not. A surplus charge neutralization hypothesis was applied to the origin of attractive intermolecular interactions between the ligands and saccharides. This idea was supported from the concomitant opposite tendency in upfield 19F-NMR and downfield 1H-NMR chemical shifts of Eu(fod)3 and the opposite Mulliken charges between F-C bonds (fod) and H-C bonds (CTA and D-/L-Glu). An analysis of CPL excitation (CPLE) and CPL spectra suggests that (+)- and (–)-sign CPL signals of EuIII and TbIII at different 4f-4f transitions in the visible region are the same with the (+)-and (–)-sign exhibited by CPLE bands at high energy levels of EuIII and TbIII in the near-UV region.

Photophysical and Chiroptical Properties of the Enantiomers of N,N'-Bis(1-phenylpropyl)-2,6-pyridinecarboxamide and their Chiral 9-Coordinate Ln3+ Complexes.

The R,R and S,S enantiomers of N,N'-bis(1-phenylpropyl)-2,6-pyridinedicarboxamide, L(Et), react with Ln3+ ions (Ln = La, Eu, Gd, and Tb) to give stable [Ln((R,R)- and (S,S)-L(Et))3]3+ in anhydrous acetonitrile solution, as evidenced by various spectroscopic measurements, including NMR and luminescence titrations. In addition to the characteristic Eu3+ and Tb3+ luminescence bands, the steady-state and time-resolved luminescence spectra of the aforementioned complexes show the residual ligand-centered emission of the 1ππ* to 3ππ* states, indicating an incomplete intersystem crossing (ISC) transfer from the 1ππ* to 3ππ* and ligand-to-Ln3+ energy transfer, respectively. The high circularly polarized luminescence (CPL) activity of [Eu(L(Et))3]3+ confirms that using a single enantiomer of L(Et) induces the preferential formation of one chiral [Eu(L(Et))3]3+ complex, consistent with the [EuL 3]3+ complexes formed with other ligands derived from a 2,6-pyridine dicarboxamide moiety. Furthermore, the CPL sign patterns of complexes with (R,R) or (S,S) enantiomer of L(Et) are consistent with the CPL sign pattern of related [LnL 3]3+ complexes with the (R,R) or (S,S) enantiomer of the respective ligands in this family.

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes.

Chiral molecules are essential for the development of advanced technological applications in spintronic and photonic. The best systems should produce large circularly polarized luminescence (CPL) as estimated by their dissymmetry factor (glum), which can reach the maximum values of −2 ≤ glum ≤ 2 when either pure right- or left-handed polarized light is emitted after standard excitation. For matching this requirement, theoretical considerations indicate that optical transitions with large magnetic and weak electric transition dipole moments represent the holy grail of CPL. Because of their detrimental strong and allowed electric dipole transitions, popular chiral emissive organic molecules display generally moderate dissymmetry factors (10−5 ≤ glum ≤ 10−3). However, recent efforts in this field show that glum can be significantly enhanced when the chiral organic activators are part of chiral supramolecular assemblies or of liquid crystalline materials. At the other extreme, chiral EuIII- and SmIII-based complexes, which possess intra-shell parity-forbidden electric but allowed magnetic dipole transitions, have yielded the largest dissymmetry factor reported so far with glum ~ 1.38. Consequently, 4f-based metal complexes with strong CPL are currently the best candidates for potential technological applications. They however suffer from the need for highly pure samples and from considerable production costs. In this context, chiral earth-abundant and cheap d-block metal complexes benefit from a renewed interest according that their CPL signal can be optimized despite the larger covalency displayed by d-block cations compared with 4f-block analogs. This essay thus aims at providing a minimum overview of the theoretical aspects rationalizing circularly polarized luminescence and their exploitation for the design of chiral emissive metal complexes with strong CPL. Beyond the corroboration that f–f transitions are ideal candidates for generating large dissymmetry factors, a special attention is focused on the recent attempts to use chiral CrIII-based complexes that reach values of glum up to 0.2. This could pave the way for replacing high-cost rare earths with cheap transition metals for CPL applications.