Luminescent lanthanide-based molecular materials: applications in photodynamic therapy.

Luminescent lanthanide molecular compounds have recently attracted attention as potential photosensitizers (PSs) for photodynamic therapy (PDT) against malignant cancer tumours because of their predictable systemic toxicity, temporospatial specificity, and minimal invasiveness. A photosensitizer exhibits no toxicity by itself, but in the presence of light and oxygen molecules, it can generate reactive oxygen species (ROS) to cause damage to proteins, nucleic acids, lipids, membranes, and organelles, which can induce cell apoptosis. This review focuses on the latest developments in luminescent lanthanide-based molecular materials as photosensitizers and their applications in photodynamic therapy. These molecular materials include lanthanide coordination complexes, nanoscale lanthanide coordination polymers, and lanthanide-based nanoscale metal-organic frameworks. In the end, the future challenges in the development of robust luminescent lanthanide molecular materials-based photosensitisers are outlined and emphasized to inspire the design of a new generation of phototheranostic agents.

Lysosome-targeting luminescent lanthanide complexes: from molecular design to bioimaging.

Lysosomes are essential acidic cytoplasmic membrane-bound organelles in human cells that play a critical role in many cellular events. A comprehensive understanding of lysosome-specific imaging can ultimately help us to design robust organelle-targeting therapeutic reagents for various underlying human diseases. Luminescent lanthanide molecular materials serve as an important and upcoming class of probes for cellular imaging applications with unique luminescent photophysical features such as sharp emission profiles from the visible to near-infrared spectral regions, long decay lifetimes, attractive quantum yields, large Stokes shifts, and a low propensity to photobleaching. For the last few years, a wide variety of lysosome-targeting luminescent lanthanide probes have been engineered and utilized for the imaging of hypochlorous acid and nitric oxide at the sub-cellular level and these advances are summarized in this review. The design strategies of lanthanide molecular probes, co-localization detection and lysosomal probity assay methods are briefly highlighted. Finally, the future challenges in the development of lysosome-targeting luminescent lanthanide complexes are outlined and emphasized to inspire the design of a new generation of organelle-targeting metal complexes.

A lysosome targetable luminescent bioprobe based on a europium ß-diketonate complex for cellular imaging applications.

Herein, we report a novel lysosome targetable luminescent bioprobe derived from a europium coordination compound, namely Eu(pfphOCH3IN)3(DDXPO) 4 [where HpfphOCH3IN = 4,4,5,5,5-pentafluoro-3-hydroxy-1-(1-(4-methoxyphenyl)-1H-indol-3-yl)pent-2-en-1-one and DDXPO = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide]. Notably, the newly designed europium complex exhibits significant quantum yield (Φoverall = 25 ± 3%) and 5D0 excited state lifetime (τ = 398 ± 3 µs) values under physiological pH (7.2) conditions when excited at 405 nm. Hence the developed europium complex has been evaluated for live cell imaging applications using mouse pre-adipocyte cell lines (3T3L1). Colocalization studies of the designed bio-probe with commercial Lysosome-GFP in 3T3L1 cells demonstrated the specific localization of the probe in the lysosome with a high colocalization coefficient (A = 0.83). Most importantly, the developed bioprobe exhibits good cell permeability, photostability and non-cytotoxicity.

Developing Intense Blue and Magenta Colors in α-LiZnBO3 : The Role of 3d-Metal Substitution and Coordination.

We describe the synthesis, crystal structures, and optical absorption spectra/colors of 3d-transition-metal-substituted α-LiZnBO3 derivatives: α-LiZn1-x MIIx BO3 (MII =CoII (0

A Highly Selective Chemosensor for Cyanide Derived from a Formyl-Functionalized Phosphorescent Iridium(III) Complex.

A new phosphorescent iridium(III) complex, bis[2',6'-difluorophenyl-4-formylpyridinato-N,C4']iridium(III) (picolinate) (IrC), was synthesized, fully characterized by various spectroscopic techniques, and utilized for the detection of CN(-) on the basis of the widely known hypothesis of the formation of cyanohydrins. The solid-state structure of the developed IrC was authenticated by single-crystal X-ray diffraction. Notably, the iridium(III) complex exhibits intense red phosphorescence in the solid state at 298 K (ΦPL = 0.16) and faint emission in acetonitrile solution (ΦPL = 0.02). The cyanide anion binding properties with IrC in pure and aqueous acetonitrile solutions were systematically investigated using two different channels: i.e., by means of UV-vis absorption and photoluminescence. The addition of 2.0 equiv of cyanide to a solution of the iridium(III) complex in acetonitrile (c = 20 µM) visibly changes the color from orange to yellow. On the other hand, the PL intensity of IrC at 480 nm was dramatically enhanced ∼5.36 × 10(2)-fold within 100 s along with a strong signature of a blue shift of the emission by ∼155 nm with a detection limit of 2.16 × 10(-8) M. The cyanohydrin formation mechanism is further supported by results of a (1)H NMR titration of IrC with CN(-). As an integral part of this work, phosphorescent test strips have been constructed by impregnating Whatman filter paper with IrC for the trace detection of CN(-) in the contact mode, exhibiting a detection limit at the nanogram level (∼265 ng/mL). Finally, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed to understand the electronic structure and the corresponding transitions involved in the designed phosphorescent iridium(III) complex probe and its cyanide adduct.

Tuning of the excitation wavelength in Eu(3+)-aminophenyl based polyfluorinated ß-diketonate complexes: a red-emitting Eu(3+)-complex encapsulated in a silica/polymer hybrid material excited by blue light.

We describe herein the synthesis, characterization and photophysical properties of a series of europium complexes based on three aminophenyl based polyfluorinated ß-diketonates, namely, 1-(4-aminophenyl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one, 1-(4-(dimethylamino)phenyl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one and 1-(4-(diphenylamino)phenyl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one, and an ancillary ligand, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide. The results demonstrated that the triphenylamine based polyfluorinated Eu(3+)-ß-diketonate complexes dramatically red-shifted the excitation maximum to the visible region (λex, max = 400 nm) with an impressive quantum yield (40%) as compared to the simple Eu(3+)-aminophenyl-ß-diketonate complexes (λex, max = 370 nm). This can be explained on the basis of the conjugation between nitrogen lone pair electrons and the phenyl π-electrons in the ß-diketonate ligand system. On the other hand, the electron-donating dimethylamino group (Hammett constant: σp = -0.83) containing Eu(3+)-ß-diketonate complexes moderately shifted the excitation maximum in the UV region from 370 to 380 nm as compared to unsubstituted aminophenyl (Hammett constant: σp = -0.66) Eu(3+) complexes. The displacement of water molecules in aminophenyl based Eu(3+)-ß-diketonate binary complexes by a rigid phosphine oxide ligand richly enhances the photoluminescence quantum yields as well as the excited state lifetime values of the corresponding ternary complexes. As an integral part of this work, hybrid materials have been developed through a sol-gel route by encapsulating a ternary Eu(3+) compound in a silica/polymer hybrid for high performance luminescence applications. In addition, a bright red-emitting diode was fabricated by coating the designed hybrid material onto a 400 nm emitting InGaN chip and the photoluminescence was examined. Notably, the current study clearly shows that the developed triphenylamine based Eu(3+)-ß-diketonate complex is an interesting red-emitting material excited by blue light and therefore may find potential applications in the fields of biological and materials science.

Amending the anisotropy barrier and luminescence behavior of heterometallic trinuclear linear [M(II) -Ln(III) -M(II) ] (Ln(III) =Gd, Tb, Dy; M(II) =Mg/Zn) complexes by change from divalent paramagnetic to diamagnetic metal ions.

The sequential reaction of a multisite coordinating compartmental ligand [2-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylideneamino)-2-methylpropane-1,3-diol] (LH4 ) with appropriate lanthanide salts followed by the addition of [Mg(NO3 )2 ]⋅6 H2 O or [Zn(NO3 )2 ]⋅6 H2 O in a 4:1:2 stoichiometric ratio in the presence of triethylamine affords a series of isostructural heterometallic trinuclear complexes containing [Mg2 Ln](3+) (Ln=Dy, Gd, and Tb) and [Zn2 Ln](3+) (Ln=Dy, Gd, and Tb) cores. The formation of these complexes is demonstrated by X-ray crystallography as well as ESI-MS spectra. All complexes are isostructural possessing a linear trimetallic core with a central lanthanide ion. The comprehensive studies discussed involve the synthesis, structure, magnetism, and photophysical properties on this family of trinuclear [Mg2 Ln](3+) and [Zn2 Ln](3+) heterometallic complexes. [Mg2 Dy](3+) and [Zn2 Dy](3+) show slow relaxation of the magnetization below 12 K under zero applied direct current (dc) field, but without reaching a neat maximum, which is due to the overlapping with a faster quantum tunneling relaxation mediated through dipole-dipole and hyperfine interactions. Under a small applied dc field of 1000 Oe, the quantum tunneling is almost suppressed and temperature and frequency dependent peaks are observed, thus confirming the single-molecule magnet behavior of complexes [Mg2 Dy](3+) and [Zn2 Dy](3+) .

Chemodosimetric cyanide sensing in a 5,15-porphodimethene Pd(II) complex.

The Pd(II) complex of 5,15-porphodimethene is shown as a chemodosimetric sensor where it selectively senses cyanide ions, monitored through electronic spectral analysis and identified by the naked eye. The possible binding mechanism is also proposed based on the (1)H NMR analyses. Two polymorphs of the mentioned complex are obtained by using different polar solvents and further confirmed by single crystal X-ray analyses.

Tunable white-light emission from mixed lanthanide (Eu³âº, Gd³âº, Tb³âº) coordination polymers derived from 4-(dipyridin-2-yl)aminobenzoate.

Herein, we have developed a series of isostructural mixed Ln(3+)-4-(dipyridin-2-yl)aminobenzoate coordination polymers [Ln(3+) = Eu(3+) (1), Tb(3+) (2), and Gd(3+) (3)], and characterized and investigated their photophysical properties. The results demonstrated that by gently tuning the excitation wavelength of these mixed lanthanide complexes, white light emission can be realized with the Commission Internationale de I'Eclairage coordinates (0.32, 0.34). Furthermore, by changing the concentration profiles of lanthanide ions stoichiometrically in mixed-lanthanide complexes and exciting at particular wavelengths, various emission colours can also be successfully obtained. The antenna ligand, 4-(dipyridin-2-yl)aminobenzoic acid, provides an efficient energy transfer for the sensitization of Eu(3+) and Tb(3+) complexes and exhibits red and green emissions, respectively. Most importantly, due to the high energy (32,150 cm(-1)) of the Gd(3+) ion lowest-lying emission level, the corresponding Gd(3+) complex displays ligand-centered visible emission in the blue light region, and hence it acts as a blue emitter. Therefore, Eu(3+) and Tb(3+) complexes in conjunction with a Gd(3+) complex is a suitable choice to obtain tunable white-light-emission from Ln(3+) coordination polymers. The morphological analyses of the mixed lanthanide coordination polymers by transmission electron microscopy (TEM) disclose that these compounds exist as unique crystalline nano-rods with an average diameter of 200 nm. The developed mixed lanthanide complexes also exhibit high thermal stability (~420 °C).

Photoenolization via excited state double proton transfer induces "turn on" fluorescence in diformyl diaryl dipyrromethane.

A light triggered enolization in diformyl diaryl dipyrromethane by excited state dual proton transfer (ESDPT) induces "turn on" fluorescence. The role of diaryl and diformyl groups in the enolization process was confirmed by photophysical and theoretical studies.

Exploring anagostic interactions in 5,15-porphodimethene metal complexes.

Using a metal templating strategy, 5,15-porphodimethene metal complexes were synthesized and their structure confirmed by single crystal X-ray analysis. The anagostic interaction causes distortion, while the hydrogen bonding interactions generate dimerisation and array formation in these complexes.

Visible-light sensitized luminescent europium(III)-ß-diketonate complexes: bioprobes for cellular imaging.

Visible-light sensitized luminescent europium(III) molecular materials are of considerable importance because their outstanding photophysical properties make them well suited as labels in fluorescence-based bioassays and low-voltage driven pure red-emitters in optoelectronic technology. One challenge in this field is development of visible-light sensitizing ligands that can form highly emissive europium(III) complexes with sufficient stability and aqueous solubility for practical applications. Indeed, some of the recent reports have demonstrated that the excitation-window can be shifted to longer-wavelengths in europium(III)-ß-diketonate complexes by appropriate molecular engineering and suitably expanded π-conjugation in the complex molecules. In this review, attention is focused on the latest innovations in the syntheses and photophysical properties of visible-light sensitized europium(III)-ß-diketonate complexes and their application as bioprobes for cellular imaging. Furthermore, luminescent nanomaterials derived from long-wavelength sensitized europium(III)-ß-diketonate complexes and their application in life sciences are also highlighted.

Brilliant photoluminescence and triboluminescence from ternary complexes of Dy(III) and Tb(III) with 3-phenyl-4-propanoyl-5-isoxazolonate and a bidentate phosphine oxide coligand.

Three new lanthanide heterocyclic ß-diketonate complexes [Dy(PPI)3(EtOH)2] (1), [Dy(PPI)3(DPEPO)] (2), and [Tb(PPI)3(DPEPO)] (3) [where HPPI = 3-phenyl-4-propanoyl-5-isoxazolone and DPEPO = bis(2-(diphenylphosphino)phenyl)ether oxide] have been synthesized and fully characterized. Single-crystal X-ray diffraction analyses reveal that these complexes are mononuclear and that the central Ln(III) ion is coordinated to eight oxygen atoms that are provided by three bidentate ß-diketonate ligands and ethanol or bidentate DPEPO in a distorted square antiprismatic geometry. These complexes have high molar absorption coefficients (up to 3 × 10(4) M(-1) cm(-1) at 285 nm) and display strong visible and, for Dy(III), NIR luminescence upon irradiation at the ligand-centered band in the range 250-350 nm. The emission quantum yields and the luminescence lifetimes at room temperature are 3 ± 0.5% and 15 ± 1 µs for 1, 12 ± 2% and 33 ± 1 µs for 2, and 42 ± 6% and 795 ± 1 µs for 3. Moreover, the crystals of 2 and 3 exhibit brilliant triboluminescence, visible in daylight.

A mitochondria-specific visible-light sensitized europium ß-diketonate complex with red emission.

Our recently developed Eu(3+) coordination compound, Eu(pfppd)3(tpy) [where Hpfppd = 4,4,5,5,5-pentafluoro-3-hydroxy-1-(phenanthren-3-yl)pentanedione and tpy = 2,2':6,6''-terpyridine] exhibits significant quantum yield (Φoverall = 41%) and long (5)D0 lifetime (880 µs) values under biologically relevant pH conditions (pH = 7.4) when excited with visible light. Hence, the Eu(3+) luminescent complex was examined for live cell imaging using the rat embryonic heart cell line, H9c2. The ternary Eu(3+) complex permeates into the H9c2 cells and co-localises with the mitochondria, as demonstrated by counterstaining experiments. Furthermore, the designed Eu(3+) bioprobe remains undissociated in the cell medium, showed a good cell permeability and a fast cellular uptake with a specific localization profile. Thus it has the potential to become a time-resolved imaging probe that is excitable in the visible-light range.

Syntheses of normal, expanded, strapped and N-confused calixbenzophyrins from a single starting material.

The syntheses and spectral and structural characterization of hitherto unknown p-benzene incorporated normal, expanded, strapped and N-confused calixbenzophyrins are achieved; altogether five new macrocycles from a single starting material are reported. The binding studies of the strapped macrocycle revealed that the molecule is selective towards Fe(III) ions.

Fluorine interaction controlled AIEE phenomenon in an expanded calixbenzophyrin and its vapoluminescent response: turn on emission with volatile ketones and esters.

Fluorine interaction assisted AIEE characteristic in an expanded calixbenzophyrin is presented by single-crystal X-ray-diffraction analysis and molecular modelling approaches. Selective exposure to volatile organic compounds such as ketones and esters results in the breaking of fluorine interaction, leading to enhanced monomer emission.

Lanthanide benzoates: a versatile building block for the construction of efficient light emitting materials.

On account of their intrinsic chemical and spectroscopic properties, luminescent lanthanide molecular materials find potential applications in lighting, optical communications, photonics and biomedical devices. This perspective article summarizes some recent seminal research work on luminescent properties and structural aspects of a series of lanthanide benzoate complexes featuring Eu(3+) and Tb(3+) ions. In particular, when modified with light-harvesting moieties, benzoates have proven to be efficient sensitizers for lanthanide ions. The photoluminescence properties of the various lanthanide benzoate coordination compounds have also been correlated with the electronic states of the newly designed antenna molecules.

Synthesis, crystal structure and photophysical properties of lanthanide coordination polymers of 4-[4-(9H-carbazol-9-yl)butoxy]benzoate: the effect of bidentate nitrogen donors on luminescence.

A new aromatic carboxylate ligand, 4-[4-(9H-carbazol-9-yl)butoxy]benzoic acid (HL), has been synthesized by the replacement of the hydroxyl hydrogen of 4-hydroxy benzoic acid with a 9-butyl-9H-carbazole moiety. The anion derived from HL has been used for the support of a series of lanthanide coordination compounds [Ln = Eu (1), Gd (2) and Tb (3)]. The new lanthanide complexes have been characterized by a variety of spectroscopic techniques. Complex 3 was structurally authenticated by single-crystal X-ray diffraction and found to exist as a solvent-free 1D coordination polymer with the formula [Tb(L)(3)](n). The structural data reveal that the terbium atoms in compound 3 reside in an octahedral ligand environment that is somewhat unusual for a lanthanide. It is interesting to note that each carboxylate group exhibits only a bridging-bidentate mode, with a complete lack of more complex connectivities that are commonly observed for extended lanthanide-containing solid-state structures. Examination of the packing diagram for revealed the existence of two-dimensional molecular arrays held together by means of CH-π interactions. Aromatic carboxylates of the lanthanides are known to exhibit highly efficient luminescence, thus offering the promise of applicability as optical devices. However, due to difficulties that arise on account of their polymeric nature, their practical application is somewhat limited. Accordingly, synthetic routes to discrete molecular species are highly desirable. For this purpose, a series of ternary lanthanide complexes was designed, synthesized and characterized, namely [Eu(L)(3)(phen)] (4), [Eu(L)(3)(tmphen)] (5), [Tb(L)(3)(phen)] (6) and [Tb(L)(3)(tmphen)] (7) (phen = 1,10-phenanthroline and tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline). The photophysical properties of the foregoing complexes in the solid state at room temperature have been investigated. The quantum yields of the ternary complexes 4 (9.65%), 5 (21.00%), 6 (14.07%) and 7 (32.42%), were found to be significantly enhanced in the presence of bidentate nitrogen donors when compared with those of the corresponding binary compounds 1 (0.11%) and 3 (1.45%). Presumably this is due to effective energy transfer from the ancillary ligands.

Highly luminescent and thermally stable lanthanide coordination polymers designed from 4-(dipyridin-2-yl)aminobenzoate: efficient energy transfer from Tb3+ to Eu3+ in a mixed lanthanide coordination compound.

Herein, a new aromatic carboxylate ligand, namely, 4-(dipyridin-2-yl)aminobenzoic acid (HL), has been designed and employed for the construction of a series of lanthanide complexes (Eu(3+) = 1, Tb(3+) = 2, and Gd(3+) = 3). Complexes of 1 and 2 were structurally authenticated by single-crystal X-ray diffraction and were found to exist as infinite 1D coordination polymers with the general formulas {[Eu(L)(3)(H(2)O)(2)]}(n) (1) and {[Tb(L)(3)(H(2)O)].(H(2)O)}(n) (2). Both compounds crystallize in monoclinic space group C2/c. The photophysical properties demonstrated that the developed 4-(dipyridin-2-yl)aminobenzoate ligand is well suited for the sensitization of Tb(3+) emission (Φ(overall) = 64%) thanks to the favorable position of the triplet state ((3)ππ*) of the ligand [the energy difference between the triplet state of the ligand and the excited state of Tb(3+) (ΔE) = (3)ππ* - (5)D(4) = 3197 cm(-1)], as investigated in the Gd(3+) complex. On the other hand, the corresponding Eu(3+) complex shows weak luminescence efficiency (Φ(overall) = 7%) due to poor matching of the triplet state of the ligand with that of the emissive excited states of the metal ion (ΔE = (3)ππ* - (5)D(0) = 6447 cm(-1)). Furthermore, in the present work, a mixed lanthanide system featuring Eu(3+) and Tb(3+) ions with the general formula {[Eu(0.5)Tb(0.5)(L)(3)(H(2)O)(2)]}(n) (4) was also synthesized, and the luminescent properties were evaluated and compared with those of the analogous single-lanthanide-ion systems (1 and 2). The lifetime measurements for 4 strongly support the premise that efficient energy transfer occurs between Tb(3+) and Eu(3+) in a mixed lanthanide system (η = 86%).

4,4,9,9-Tetraphenyl pyrroloindolizine: a structural analogue of calix[2]pyrrole.

Synthesis, spectral and structural characterization of a pyrroloindolizine derivative having structural similarity with calix[2]pyrrole is described. Here, two pyrrole rings are connected with two meso-carbon atoms having an N,α-linkage and an α,ß-linkage to afford the smallest analogue in the calixpyrrole family. Detailed NMR spectroscopic studies along with single crystal X-ray analysis confirm the assigned structure of the molecule.