Guest-Responsive Near-Infrared-Luminescent Metal-Organic Cage Organized by Porphyrin Dyes and Yb(III) Complexes.

Metal-organic cages (MOCs) with luminophores have significant advantages for the facile detection of specific molecules based on turn-on or turn-off luminescence changes induced by host-guest complexation. One important challenge is the development of turn-on-type near-infrared (NIR)-luminescent MOCs. In this study, we synthesized a novel MOC consisting of two porphyrin dyes linked by four Yb(III) complexes, which exhibit bimodal red and NIR fluorescence signals upon photoexcitation of the porphyrin π system. Single-crystal X-ray structural analysis and computational molecular modeling revealed that planar aromatic perfluorocarbons were intercalated into the MOC. The tight packing between the MOC and guests enhanced the NIR fluorescence of Yb(III) by suppressing energy transfer from the photoexcited porphyrin to oxygen molecules. Guest-responsive turn-on NIR fluorescence changes in an MOC were successfully demonstrated.

Highly Efficient and Thermally Durable Luminescence of 1D Eu3+ Coordination Polymers with Arsenic Bridging Ligands.

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one-dimensional (1D) Eu3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating-induced emission enhancement observed when the temperature was increased from 300 K to 400 K.

Effective photosensitized emission of a Tb(III) complex using a ß-diketonate photosensitizer and an oxygen barrier system in a thermally populated triplet state.

Photosensitizer design of luminescent terbium (Tb(III)) complexes with narrow bandwidths is important for advancing luminescent materials. In this study, we report an effective photosensitizer model in a thermally populated lowest excited triplet (T1) state during Tb(III) emission. The Tb(III) complex comprises a Tb(III) ion (serving as an emission center), hexafluoroacetylacetonates (acting as photosensitizer ligands), and bulky cyclohexyl group-attached phosphine-oxide-type ligands (functioning as an oxygen barrier system). Emission properties including emission and excitation spectra, ligand-excited emission quantum yields, and emission lifetimes were evaluated in the absence and presence of oxygen. Coordination geometry structures were determined through analysing single-crystal structures. The electronic structure based on 4f-orbitals was estimated from radiative rate constants and quantum chemical calculations. The bulky phosphine oxide ligand not only provides an oxygen barrier system but also induces an electronic structural modulation based on 4f-orbitals, allowing for effective photosensitized Tb(III) emission in a thermally populated ligand T1 state in air.

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.

Current Development of Lanthanide Complexes for Biomedical Applications.

Luminescent molecule-based bioimaging system is widely used for precise localization and distinction of cancer/tumor cells. Luminescent lanthanide (Ln(III)) complexes offer long-lived (sub-millisecond time scale) and sharp (FWHM <10 nm) emission, arising from the forbidden 4f-4f electronic transitions. Luminescent Ln(III) complex-based bioimaging has emerged as a promising option for both in vitro and in vivo visualizations. In this mini-review, the historical development and recent significant progress of luminescent Ln(III) probes for bioapplications are introduced. The recent studies are mainly focused on three points: (i) the structural modifications of Ln(III) complexes in both macrocyclic and small ligands, (ii) the acquirement of high resolution luminescence images of cancer/tumor cells and (iii) the constructions of ratiometric biosensors. Furthermore, our recent study is explained as a new Cancer GPS (cancer grade probing for determining tumor grade through photophysical property analyses of intracellular Eu(III) complex.

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.

Structure-changeable luminescent Eu(III) complex as a human cancer grade probing system for brain tumor diagnosis.

Accurate determination of human tumor malignancy is important for choosing efficient and safe therapies. Bioimaging technologies based on luminescent molecules are widely used to localize and distinguish active tumor cells. Here, we report a human cancer grade probing system (GPS) using a water-soluble and structure-changeable Eu(III) complex for the continuous detection of early human brain tumors of different malignancy grades. Time-dependent emission spectra of the Eu(III) complexes in various types of tumor cells were recorded. The radiative rate constants (kr), which depend on the geometry of the Eu(III) complex, were calculated from the emission spectra. The tendency of the kr values to vary depended on the tumor cells at different malignancy grades. Between T = 0 and T = 3 h of invasion, the kr values exhibited an increase of 4% in NHA/TS (benign grade II gliomas), 7% in NHA/TSR (malignant grade III gliomas), and 27% in NHA/TSRA (malignant grade IV gliomas). Tumor cells with high-grade malignancy exhibited a rapid upward trend in kr values. The cancer GPS employs Eu(III) emissions to provide a new diagnostic method for determining human brain tumor malignancy.

Sandglass-Typed Single Chameleon Luminophore for Water Mapping Measurements: Intramolecular Energy Migrations in the Hydrophilic Tb(III)/Sm(III) Cluster.

Novel hydrophilic and color-changeable single chameleon luminophores composed of Tb(III)/Sm(III) nona-nuclear clusters [TbxSm9-x(Sal-PEG-n)16(µ-OH)10]+(NO3)- (x = 1, 2, 3, and 9; Sal-PEG-n: salicylate polyethylene glycolmethylester, n = 2 and 4) are reported for water mapping measurements. Their characteristic sandglass structures and aggregates were analyzed using X-ray single crystal analysis and dynamic light scattering (DLS) measurements. The green- and yellow-luminescence of [Tb3Sm6(Sal-PEG-4)16(µ-OH)]+(NO3)- in water were observed at 20 and 50 °C, respectively. The ratio-metric luminescence analysis using green Tb(III) and orange Sm(III) emission bands is a promising candidate for exact temperature distribution measurements in fluid dynamics. The effective temperature-sensing property based on the competitive intramolecular energy transfer processes between Tb(III)-to-ligand and Tb(III)-to-Sm(III) in a non-a-nuclear cluster is explained using temperature-dependent kinetic analyses in the excited state.

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.

Highly efficient light harvesting of a Eu(iii) complex in a host-guest film by triplet sensitization.

Trivalent lanthanide complexes are attractive light emitters owing to their ideal high color purity. Sensitization using ligands with high absorption efficiency is a powerful approach to enhancing photoluminescence intensity. However, the development of antenna ligands that can be used for sensitization is limited due to difficulties in controlling the coordination structures of lanthanides. When compared to conventional luminescent Eu(iii) complexes, a system composed of triazine-based host molecules and Eu(hfa)3(TPPO)2 (hfa: hexafluoroacetylacetonato and TPPO: triphenylphosphine oxide) significantly increased total photoluminescence intensity. Energy transfer from the host molecules to the Eu(iii) ion occurs via triplet states over several molecules, according to time-resolved spectroscopic studies, with nearly 100% efficiency. Our discovery paves the way for efficient light harvesting of Eu(iii) complexes with simple fabrication using a solution process.

Thermally-assisted photosensitized emission in a trivalent terbium complex.

Luminescent lanthanide complexes containing effective photosensitizers are promising materials for use in displays and sensors. The photosensitizer design strategy has been studied for developing the lanthanide-based luminophores. Herein, we demonstrate a photosensitizer design using dinuclear luminescent lanthanide complex, which exhibits thermally-assisted photosensitized emission. The lanthanide complex comprised Tb(III) ions, six tetramethylheptanedionates, and phosphine oxide bridge containing a phenanthrene frameworks. The phenanthrene ligand and Tb(III) ions are the energy donor (photosensitizer) and acceptor (emission center) parts, respectively. The energy-donating level of the ligand (lowest excited triplet (T1) level = 19,850 cm-1) is lower than the emitting level of the Tb(III) ion (5D4 level = 20,500 cm-1). The long-lived T1 state of the energy-donating ligands promoted an efficient thermally-assisted photosensitized emission of the Tb(III) acceptor (5D4 level), resulting in a pure-green colored emission with a high photosensitized emission quantum yield (73%).

Characteristic stacked structures and luminescent properties of dinuclear lanthanide complexes with pyrene units.

A novel design strategy of stacked organic fluorophores using dinuclear lanthanide (Ln(III)) complexes is demonstrated for the formation of excimer. The dinuclear Ln(III) complexes are composed of two Ln(III) (Eu(III) or Gd(III)) ions, six hexafluoroacetylacetonate (hfa), and two pyrene-based phosphine oxide ligands. Single-crystal analysis revealed a rigid pyrene-stacked structure via CH-F (pyrene/hfa) intramolecular interactions. The rigid aggregation structures of the two-typed organic ligands around Ln(III) resulted in high thermal stability (decomposition temperature: 340°C). The aggregated ligands exhibited excimer-type green emission from the stacked pyrene-center. The change in the Ln(III) ion promotes effective shifts of excimer emissions (Gd(III):500 nm, Eu(III):490 nm). The organic aggregation system using red-luminescent Eu(III) also provides temperature-sensitive ratiometric emission composed of π-π* and 4f-4f transitions by energy migration between aggregated ligands and Eu(III).

Structural metamorphosis and photophysical properties of thermostable nano- and microcrystalline lanthanide polymer with flexible coordination chains.

Luminescent lanthanide coordination polymer crystals (LCPCs) represent an area of growing interest in materials chemistry owing to their unique and tailorable functional properties. The LCPCs provide a high level of structural tunability, including size- and morphology-dependent properties; therefore, they are promising materials for next-generation phosphors in a wide range of applications such as light emitting diodes. Here, by controlling the morphology of thermostable europium coordination polymer crystals, [Eu(hfa)3(dpbp)]n, hfa: hexafluoroacetylacetonate and dpbp:4,4'-bis(diphenyl　phosphoryl) biphenyl), we realized a novel red phosphor with narrow linewidth emission (FWHM = 7.8 nm). The obtained luminescent LCPCs with unique structures were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and thermogravimetric analysis. Among, them, size tunable crystalline polymer spheres were found to have high internal quantum efficiency (ex., IQE = 79%) and highly thermostability (>300°C), and to exhibit dispersibility in PMMA media. The obtained results on the structural tunability of these materials can be used for the development of synthesis techniques for nanoscale materials based on crystalline lanthanide-based coordination phosphors.

Luminescent Lanthanide Complexes for Effective Oxygen-Sensing and Singlet Oxygen Generation.

Invited for this month's cover are the collaborating groups of Yuichi Kitagawa, Yasuchika Hasegawa, and co-workers at the Hokkaido University. The cover picture shows triplet-oxygen sensing and singlet-oxygen generation using lanthanide complexes. Organic ligands play crucial roles in lanthanide complexes as light-harvesting antennas for lanthanide luminescence and singlet-oxygen generation. More information can be found in the Review by Y. Kitagawa, Y. Hasegawa, and co-workers.

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.

Luminescent Lanthanide Complexes for Effective Oxygen-Sensing and Singlet Oxygen Generation.

Oxygen quantification using luminescence has attracted considerable attention in various fields, including environmental monitoring and clinical analysis. Among the reported luminophores, trivalent lanthanide complexes have displayed characteristic narrow emission bands with high brightness. This bright emission is based on photo-sensitized energy transfer via organic triplet states. The organic triplet states in lanthanide complexes effectively react with the triplet oxygen, enabling oxygen quantification by lanthanide luminescence. Some TbIII and EuIII complexes with slow deactivation processes have also formed the excited state equilibrium, thus resulting in the emission-lifetime based oxygen sensing property. The combination of TbIII /EuIII emission, EuIII /SmIII emission, EuIII /ligand phosphorescence, and ligand fluorescence/ligand phosphorescence provide the ratiometric oxygen-sensing properties. Moreover, the reaction generates singlet oxygen species which exhibit numerous applications in the photo-medical field. The ligands with large π-conjugated aromatic systems, such as porphyrin, phthalocyanine, and polyaromatic compounds, induces highly efficient oxygen generation. The combination of effective luminescence with singlet-oxygen generation by the lanthanide complexes render them suitable for photo-driven theranostics. This review summarizes the research progress of lanthanide complexes with efficient oxygen-sensing and singlet-oxygen generation properties.

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.

Plant growth acceleration using a transparent Eu3+-painted UV-to-red conversion film.

The stimulation of photosynthesis is a strategy for achieving sustainable plant production. Red light is useful for plant growth because it is absorbed by chlorophyll pigments, which initiate natural photosynthetic processes. Ultraviolet (UV)-to-red wavelength-converting materials are promising candidates for eco-friendly plant cultures that do not require electric power. In this study, transparent films equipped with a UV-to-red wavelength-converting luminophore, the Eu3+ complex, were prepared on commercially available plastic films for plant growth experiments. The present Eu3+-based films absorb UV light and exhibit strong red luminescence under sunlight. Eu3+-painted films provide significant growth acceleration with size increment and biomass production for vegetal crops and trees in a northern region. The plants cultured with Eu3+-painted films had a 1.2-fold height and 1.4-fold total body biomass than those cultures without the Eu3+ luminophores. The present film can promote the plant production in fields of agriculture and forestry.

Emission Properties of Eu(III) Complexes Containing Arsine and Phosphine Ligands with Annulated Structures.

In this study, we synthesized Eu3+ complexes containing arsine and phosphine oxides with annulated structures as the antenna ligands. The type of bridging in the annulated structures controlled the energy level of the triplet excited state and the intersystem crossing efficiency, leading to different emission properties. Eu3+ complexes bearing the arsine oxides showed a higher intensity ratio of electric/magnetic dipole transitions and energy-transfer efficiency than the complexes with the corresponding phosphine oxides.