Chiral Tetrakis Eu(III) Complexes with Ammonium Cations for Improved Circularly Polarized Luminescence.

Large dissymmetry factor of the circularly polarized luminescence (gCPL) was observed in ligand and coordination tuned chiral tetrakis europium (Eu(III)) complexes with ammonium cations. The gCPL value was estimated to be -1.54, which is the largest among chiral luminescent molecules. Through photophysical measurements, single crystal X-ray structural analyses and quantum chemical calculations, changes in the geometric and electronic structures were observed for a series of chiral tetrakis Eu(III) complexes which enhanced the gCPL value. The emission quantum yield and photosensitized energy transfer efficiencies of chiral Eu(III) complexes with ammonium cations were also larger than that with previous Cs+. Based on the systematic modifications and analyses for chiral tetrakis Eu(III) complex, effect of the ammonium cation on enhanced CPL brightness is reported.

Circularly polarized luminescence and high photoluminescence quantum yields from rigid 5,10-dihydroindeno[2,1-a]indene and 2,2'-dialkoxy-1,1'-binaphthyl conjugates and copolymers.

5,5,10,10-Tetramethyl-5,10-dihydroindeno[2,1-a]indene (COPV1(Me)) was installed into either the 3,3'- or 6,6'-positions of chiral 2,2'-dioctyloxy-1,1'-binaphthyl to afford 2 : 1 conjugates (monomeric compounds) and 1 : 1 copolymers. These compounds showed high photoluminescence quantum yields of >0.95 whilst also exhibiting circular dichroism (CD) and circularly polarized luminescence (CPL). The dissymmetry factors of CPL (gCPL) for the 3,3'- and 6,6'-monomeric compounds in THF were 6.6 × 10-4 and 3.3 × 10-4, respectively. The 3,3'-isomer has a higher g value than the 6,6'-isomer, which was attributed to the difference in the extent of π-conjugation and the angle between electronic and magnetic transition moments. The gCPL values of the 3,3'-linked and 6,6'-linked copolymers were 1.1 × 10-3 and 6.8 × 10-4, respectively. The structural rigidity of the COPV units is beneficial to achieve relatively high g values whilst maintaining a photoluminescence quantum yield that is close to unity by using a single type of fluorophore.

Rapid Synthesis of Chiral Figure-Eight Macrocycles Using a Preorganized Natural Product-Based Scaffold.

Chiral D2 -symmetric figure-eight shaped macrocycles are promising scaffolds for amplifying the chiroptical properties of π-conjugated systems. By harnessing the inherent and adaptable conformational dynamics of a chiral C2 -symmetric bispyrrolidinoindoline (BPI) manifold, we developed an enantio-divergent modular synthetic platform to rapidly generate a diverse range of chiral macrocycles, spanning from 14- to 66-membered rings, eliminating the need for optical resolution. Notably, a 32-membered figure-eight macrocycle showed excellent circularly polarized luminescence (CPL: |glum |=1.1×10-2 ) complemented by a robust emission quantum yield (Φfl =0.74), to achieve outstanding CPL brightness (BCPL : ϵ×Φfl ×|glum |/2=480). Using quadruple Sonogashira couplings, this versatile synthetic platform enables precise adjustments of the angle, distance, and length among intersecting π-conjugated chromophores. Our synthetic strategy offers a streamlined and systematic approach to significantly enhance BCPL values for a variety of chiral D2 -symmetric figure-eight macrocycles.

Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries.

We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (fac-4 (fac-Ir(ppyCO2H)3 (ppy: 2-phenylpyridine)), fac-6 (fac-Ir(tpyCO2H)3 (tpy: 2-(4'-tolyl)pyridine)), and fac-13 (fac-Ir(mpiqCO2H)3 (mpiq: 1-(4'-methylphenyl)isoquinoline))) were converted into the diastereomers, Δ- and Λ-forms of fac-9 (from fac-6), fac-10 (from fac-4), fac-11 (from fac-6), and fac-14 (from fac-13), respectively, by the condensation with (1R,2R)-1,2-diaminocyclohexane or (1R,2R)-2-aminocyclohexanol. The resulting diastereomers were separated by HPLC (with a nonchiral column) or silica gel column chromatography, and their absolute stereochemistry was determined by X-ray single-crystal structure analysis and CD (circular dichroism) spectra. Spectra of all diastereomers of the Ir(III) complexes are reported. Hydrolysis of the ester moieties of Δ- and Λ-forms of fac-10, fac-11, and fac-14 gave both enantiomers of the corresponding carboxylic acid derivatives in the optically pure forms, Δ-fac and Λ-fac-4, -6, and -13, respectively.

Synthesis of Bicyclo[1.1.1]pentane (BCP)-Based Straight-Shaped Diphosphine Ligands.

[1.1.1]Propellane, which is structurally simple and compact, exhibits promising potential for the synthesis of disubstituted straight-shaped bicyclo[1.1.1]pentane (BCP) compounds by manipulation of its highly reactive internal C-C bond. BCPs are considered to be isosteres of 1,4-disubstituted benzenes, which have found broad applications in the areas of functional molecules and drug discovery. The internal C-C single bond of [1.1.1]propellane is regarded as a charge-shift bond, which can be readily cleaved by radical means to construct BCPs. We herein report a novel synthetic method for (un)symmetric diphosphines based on the BCP motif, which can be interpreted as isosteres of 1,4-bis(diphenylphosphino)benzenes. The obtained BCP-diphosphine derivatives were used to generate a straight-shaped Au complex and an Eu-based coordination polymer.

Enhanced circularly polarized luminescence of chiral Eu(III) coordination polymers with structural strain.

Three types of Eu(III) coordination polymers with different distorted chiral ligands, [Eu(+tfc)3(p-dpeb)]n, [Eu(+pfc)3(p-dpeb)]n, and [Eu(+hfc)3(p-dpeb)]n (+tfc: (+)-3-(trifluoroacetyl)camphorate, +pfc: (+)-3-(pentafluoropropionyl)camphorate, +hfc: (+)-3-(heptafluorobutyryl)camphorate, p-dpeb: 1,4-bis(diphenylphosphorylethynyl)benzene), were prepared for elucidating the relationship between their structural distortions, ligand-to-metal charge transfer (LMCT), and circularly polarized luminescence (CPL) properties. Their strain factors in the ligands were evaluated using crystallographic data obtained by single-crystal X-ray structural analyses. The characteristics of the LMCT excited states were estimated from theoretical calculations. The introduction of a bulky substituent into the chiral ligand afforded a distorted structure of ß-diketonates and changed the direction of the transition electric dipole moments, which are related to the magnitude of the CPL intensity. The CPL dissymmetry factor (gCPL) of [Eu(+hfc)3(p-dpeb)]n, with a large distorted structure, was -0.22, while those of [Eu(+tfc)3(p-dpeb)]n and [Eu(+pfc)3(p-dpeb)]n, with small distorted structures, were -0.05 and -0.10, respectively. The controlled steric hindrance of the chiral ligands in Eu(III) coordination polymers is one of the strain factors enhancing their CPL properties.

Asymmetric Lumino-Transformer: Circularly Polarized Luminescence of Chiral Eu(III) Coordination Polymer with Phase-Transition Behavior.

A chiral Eu(III) coordination polymer with phase-transition behavior, [Eu(+tfc)3(m-dpeb)]n, (+tfc: (+)-3-trifluoroacetylcamphorato, m-dpeb: 1,3-bis(diphenylphosphorylethynyl)benzene) was reported for understanding the effect of polymer chain arrangement (orientation effect) on the circularly polarized luminescence (CPL) in a solid system. The phase-transition behavior of the transformable Eu(III) coordination polymer was characterized using differential scanning calorimetry and powder X-ray diffraction. The Eu(III) coordination polymer exhibited phase transition at approximately 180 °C. The magnitude of the CPL intensity was drastically changed because of the phase transition, without coordination geometrical change around the Eu(III) ion. In this study, the orientation effect of a chiral Eu(III) coordination polymer on the CPL properties in crystalline solid is demonstrated.

Strong circularly polarized luminescence of mixed lanthanide coordination polymers with control of 4f electronic structures.

This paper reports chiral mixed Eu(iii)-Ln(iii) coordination polymers (Ln = Gd and Sm) with a high dissymmetry factor of circularly polarized luminescence (gCPL = 0.15) for the enhancement of the emission quantum yield (Φtot ≥ 50%), achieved via control of 4f electronic structures.

Long-wavelength visible to near infrared photoluminescence from carbon-bridged styrylstilbene and thiadiazole conjugates in organic and aqueous media.

Donor-acceptor-donor conjugates composed of electron-donating carbon-bridged styrylstilbene (COPV2) and electron-accepting thiadiazole derivatives equipped with carbazolyl (Cz) terminators, Cz-COPV2-A-COPV2-Cz (A = benzothiadiazole (BTz), naphthobis(thiadiazole) (NTz), or benzobis(thiadiazole) (BBTz)), were newly synthesized and found to serve as efficient and stable long-wavelength photoluminescent dyes in organic and aqueous media. In particular, Cz-COPV2-BBTz-COPV2-Cz showed photoluminescence in the near infrared region (895-927 nm) with a photoluminescence quantum yield (PLQY) of up to 0.19 in cyclohexane and of 0.02-0.03 in THF/water mixtures. Its analogues with weaker acceptors, Cz-COPV2-BTz-COPV2-Cz and Cz-COPV2-NTz-COPV2-Cz, showed yellow to deep-red emission in organic solvents, with PLQYs of up to 0.71 in organic solvents and 0.45 in THF/water mixtures.

Bright red emission with high color purity from Eu(iii) complexes with π-conjugated polycyclic aromatic ligands and their sensing applications.

Eu(iii) complexes emit red light with a high color purity and have consequently attracted attention for development toward display and physical sensing applications. The characteristic pure color emission originates from the intra-4f-4f transition, and the brightness strongly depends on the electronic and steric structures of organic ligands. A large π-conjugated ligand design with a large absorption coefficient has been actively studied for achieving bright emission. The π-conjugated Eu(iii) luminophores also provide oxygen and temperature sensing properties by controlling their excited state dynamics based on π-electron systems. A comprehensive understanding of the design strategy of large π-conjugated ligands is crucial for the further development of luminescent Eu(iii) complexes. In this review, we summarize the research progress on π-conjugated Eu(iii) luminophores exhibiting bright emission and their physical sensing applications.

Circularly Polarized Absorption and Luminescence of Semiconductor Eu-OCN Nanocrystals in the Blue Region of the Electromagnetic Spectrum.

Semiconductor nanomaterials with efficient polarized-light control in the blue region of the visible spectrum are promising candidates for modern and future photo-information technology, display devices, and optical sensing applications. New-type semiconductor Eu(OCN)2 nanocrystals with circularly polarized absorption (CD: circular dichroism) and emission (CPL: circularly polarized luminescence) under an applied magnetic field are demonstrated here for the first time. The effective CD signal at 1.6 T was observed at approximately 440 nm. The dissymmetry factor of CPL under 100 K, gM-CPL, was estimated to be 0.01. These characteristic circularly polarized absorption and emission phenomena of Eu(OCN)2 nanocrystals should be caused by combination between the "Faraday A and C terms" of the magnetic moment in the excited state. Polarized-light control using Eu(OCN)2 nanocrystals in the blue-light region of the electromagnetic spectrum is a large first step into a new world of photo-functional semiconductor nanomaterials.

Electronic strain effect on Eu(iii) complexes for enhanced circularly polarized luminescence.

Luminescent Eu(iii) complexes with point-chiral phosphine oxide ligands, [Eu(hfa)3((R,R)-B2QPO)] (hfa: hexafluoroacetylacetonato, B2QPO: 2,3-bis(tert-butylmethylphosphine oxide)quinoxaline) and [Eu(hfa)3((R)-B3QPO)] (B3QPO: 2-tert-butylmethylphosphine oxide-3-(di-tert-butylphosphineoxide)quinoxaline), are reported for the investigation of the electronic strain effect on the coordination sphere. Single crystal X-ray crystallography reveals the strong structural strain of the hfa ligands in [Eu(hfa)3((R,R)-B2QPO)]. The emission quantum yields of [Eu(hfa)3((R,R)-B2QPO)] in solution (55%) and solid (63%) are comparable to those of previously reported bright luminescent Eu(iii) complexes. The chiroptical properties of [Eu(hfa)3((R,R)-B2QPO)] and [Eu(hfa)3((R)-B3QPO)] were characterized using circular dichroism (CD) and circularly polarized luminescence (CPL) spectra. The dissymmetry factor of [Eu(hfa)3((R,R)-B2QPO)] was estimated to be 0.08. The chiroptical phenomena of the Eu(iii) complexes are closely related to their structural (geometry) and electronic (LMCT: ligand-to-metal charge transfer) strains.

Steric and Electronic Control of Chiral Eu(III) Complexes for Effective Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL) is characterized by the differential emission of right and left circularly polarized light by a chiral molecule. This mini-review describes the recent developments in chiral trivalent europium (Eu(III)) complexes with effective CPL. CPL has many potential applications in security tags, lasers, and three-dimensional organic electroluminescence devices, which is one of the most intensely investigated topics in molecular luminophores. Eu(III) complexes have attracted considerable attention as effective CPL luminophores for the above-mentioned applications. In this review, recent studies on the Eu(III) CPL, including the steric (dimer, tetramer, aggregates, and coordination polymers) and electronic control (mononuclear) of Eu(III) complexes for the construction of a luminophore with effective CPL, are discussed. The characteristic CPL applications employing the chiral mononuclear Eu(III) complexes are also described. Chiral Eu(III) complexes with well-designed organic ligands can result in the establishment of new research areas in the fields of photochemistry and materials science.

Luminescent Coordination Polymers Constructed from a Flexible, Tetradentate Diisopyrazole Ligand and Copper(I) Halides.

One- and two-dimensional coordination polymers composed of a structurally flexible, tetradentate diisopyrazole ligand and copper(I) halides were synthesized as crystalline solids. Complexation with copper(I) chloride or bromide resulted in the formation of infinite coordination chains through connecting each diisopyrazole ligand with two copper(I) ions in a trigonal planar coordination geometry. Contrarily, the combination of a diisopyrazole ligand and copper(I) iodide gave a two-dimensional coordination network comprising Cu4 I4 units with stair-step type geometry and diisopyrazoles that acted as both tetradentate and bidentate bridging ligands. All the coordination polymers exhibited visible photo-emission upon UV irradiation, and the Cu4 I4 complex showed thermochromic behavior.