Yb Complexes Research Articles

Synthesis, characterization, DNA binding and anticancer ability of a Yb (III) complex constructed by 1,4-bis(pyrazol-1-yl)terephthalic acid

The novel Yb(III) complex based on 1,4-bis(pyrazol-1-yl)terephthalic acid(H2L) which was synthesized and characterized. The interactions of the complex with fish sperm DNA(FS-DNA) was explored using UV absorption and fluorescence spectra analyses methods. The experimental results showed that the complex could bind to DNA via an intercalative mode. Flow cytometric analysis indicated that this complex induced apoptosis of HeLa (human cervix epithelia carcinoma cells) tumor cell lines. Moreover, MTT results indicated that complex 1 exhibited the greatest antitumor activities against the tested cell lines HeLa, with an IC50 values 13.51 ± 2.08 μM.

Synthesis and NIR photoluminescence studies of novel Yb(III) complexes of asymmetric perfluoryl β-diketone

The four new NIR emitting Yb3+ complexes using, perfluorinated β-diketone (5,5,6,6,7,7,7-heptafluoro-2,2-dimethyl-3,5-octanedione, Hfod) as main chromophore and N- / O- containing neutral heterocyclic bases namely: trispyridyl triazine (tptz) (1), indazole (2), triphenyl phosphine oxide (tppo) (3) and 4,4′-bipyridyl (4,4′ -bpy) (4) as ancillary ligands have been successfully designed. The complexes, [Yb(fod)3(L)n] (n = 1 for tptz, 4,4′-bpy and indazole and 2 for tppo) have been thoroughly characterized by elemental analysis, TGA-DTA, IR and UV–Vis spectroscopy. The complexes display efficient ligand-sensitized near-infrared luminescence from ytterbium at 925–1075 nm with lifetimes and quantum yields as high as 13 μs and 0.65%, in the solid state, and 12.35 μs and 0.62% in CHCl3 solution, respectively. The effect of ancillary ligand triplet states on the emission intensity of Yb3+ is discussed.

Near-infrared excited cooperative upconversion in luminescent Ytterbium(ΙΙΙ) bioprobes as light-responsive theranostic agents

Near-infrared (NIR) Ytterbium(ΙΙΙ) complexes namely [Yb(dpq)(DMF)2Cl3] (1), [Yb(dppz)(DMF)2Cl3] (2), [Yb(dpq)(ttfa)3] (3) and [Yb(dppz)(ttfa)3] (4) based on photosensitizing antenna: dipyrido-[3,2-d:2′,3′-f]-quinoxaline (dpq), dipyrido-[3,2-a:2′,3′-c]-phenazine (dppz) and 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Httfa), were designed as NIR bioimaging agents utilizing cooperative upconversion luminescence (CUCL) of Yb(III). Their structures, detailed photophysical properties, biological interactions, photo-induced DNA cleavage, NIR photocytotoxicity and cellular internalization and bioimaging properties were examined. Discrete mononuclear complexes adopt a seven-coordinated {LnN2O2Cl3} mono-capped octahedron (1, 2) and eight-coordinated {LnN2O6} distorted square antiprism geometry (3, 4) with bidentate N, N-donor dpq, dppz and O,O-donor ttfa ligands. The designed Yb(III) probes (3, 4) having advantages of dual sensitizing antennae (dpq/dppz and Httfa) to modulate the desirable optical properties in NIR region for bioimaging in biologically transparent window and light-responsive intracellular damage with spatiotemporal control. The lack of inner-sphere water (q = 0), remarkable photostability, large Stokes' shifts, presence of energetically rightly poised ligand 3T states allows efficient energy transfer (ET) to the emissive 2F5/2 state of Yb(ΙΙΙ). The unique cooperative upconversion luminescence (CUCL) of Yb(III) was observed in 1–4 in the visible blue region (λem = 490 nm) upon NIR excitation at 980 nm, makes them special candidates for NIR-to-visible or NIR-to-NIR cellular imaging probes. The CUCL property of Yb(III) were observed in the discrete mononuclear complexes both in solid state and solution. We elegantly utilized this remarkable property of Yb(III) for cellular imaging application for the first time to the our knowledge including potential uses in CUC/multiphoton excitation microscopy. The complexes exhibit significant binding propensity to DNA, HSA and BSA (K ∼ 105 M−1). They effectively cleave supercoiled (SC) DNA to its nicked circular (NC) form at 365 nm via photoredox pathways. The cellular uptake studies evidently displayed cytosolic and nuclear localization of the complexes. Finally, the capability of Yb(III) complexes usage for PDT were demonstrated through significant near-IR photocytotoxicity at 980 nm CW laser. The results depicted here offers an intelligent strategy towards developing light-responsive highly photostable Yb(III) probes for NIR theranostic application in the biologically transparent phototherapeutic window.

Quantitative Sensitization Efficiencies in NIR-Emissive Homoleptic Ln(III) Complexes Using 2-(5-Methylpyridin-2-yl)-8-hydroxyquinoline.

A series of isostructural lanthanide complexes [Ln(MPQ)3] (Ln = Nd, Gd, Er, Yb, Lu) using a monoanionic tridentate methylpyridyl-substituted 8-hydroxyquinoline ligand (MPHQ = 2-(5-methylpyridin-2-yl)-8-hydroxyquinoline) have been prepared and characterized using elemental analysis (CHN), single-crystal X-ray diffraction (XRD), and 1H NMR spectroscopy. This ligand forms homoleptic charge-neutral lanthanide complexes with three coordinated ligands arranged in an "up-up-down" fashion around the metal center. The photophysical properties of the Nd, Er, and Yb complexes were investigated using absorption and emission spectroscopy, with the latter species displaying efficient sensitization in the Near Infra-Red (NIR) region and a photoluminescence quantum yield (PLQY) as high as 1.0% in CH2Cl2 solution. The intersystem crossing and energy-transfer processes involved in the antenna effect were further investigated using transient absorption techniques, which revealed essentially quantitative sensitization efficiencies for the NIR-emitting cations.

Synthesis of reduced graphene oxide/macrocyclic ytterbium complex nanocomposites and their application in the counter electrodes of dye-sensitized solar cells

Abstract This study focused on synthesizing graphene oxide (GO) and macrocyclic ytterbium (Yb) complexes. The GO/Yb nanocomposite materials were prepared by performing a reaction between the secondary ammonium of macrocyclic ytterbium complexes and the GO surface functional groups (e.g., epoxide and carboxyl groups), thereby inducing the macrocyclic ytterbium complexes to uniformly cover the surface of the GO samples. In this study, different proportions of GO and macrocyclic ytterbium complexes were prepared as counter electrode (CE) materials in DSSCs; the surface morphology of the films, the composition of the structural elements, and their effects on the DSSC efficiency were discussed. The results of different analyses confirmed that a new GO/Yb nanocomposite material has been successfully synthesized in this study. Furthermore, various DSSC CEs were fabricated using different proportions of GO/Yb, and the characteristics of the DSSCs were analyzed. The results showed that the highest efficiency of the devices was 7.90%, which was higher than that of DSSCs with traditional Pt CEs. The GO/Yb nanocomposite materials can replace Pt as a CE material for DSSCs, and among all DSSC CEs prepared in this study, the DSSC with a GO/Yb (1:10) CE was the most efficient.

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

The reactions of hydrated lanthanide(III) [Ln(III)] nitrates and salicylideneaniline (salanH) have provided access to two families of mononuclear complexes depending on the reaction solvent used. In MeCN, the products are [Ln(NO3)3(salanH)2(H2O)]·MeCN, and, in MeOH, the products are [Ln(NO3)3(salanH)2(MeOH)]·(salanH). The complexes within each family are proven to be isomorphous. The structures of complexes [Ln(NO3)3(salanH)2(H2O)]·MeCN (Ln = Eu, 4·MeCN_Eu, Ln = Dy, 7·MeCN_Dy; Ln = Yb, 10·MeCN_Yb) and [Ln(NO3)3(salanH)2(MeOH)]·(salanH) (Ln = Tb, 17_Tb; Ln = Dy, 18_Dy) have been solved by single-crystal X-ray crystallography. In the five complexes, the LnIII center is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms from the two monodentate zwitterionic salanH ligands, and one oxygen atom from the coordinated H2O or MeOH group. The salanH ligands are mutually “cis” in 4·MeCN_Eu, 7·MeCN_Dy and 10·MeCN_Yb while they are “trans” in 17_Tb and 18_Dy. The lattice salanH molecule in 17_Tb and 18_Dy is also in its zwitterionic form with the acidic H atom being clearly located on the imine nitrogen atom. The coordination polyhedra defined by the nine oxygen donor atoms can be described as spherical tricapped trigonal prisms in 4·MeCN_Eu, 7·MeCN_Dy, and 10·MeCN_Yb and as spherical capped square antiprisms in 17_Tb and 18_Dy. Various intermolecular interactions build the crystal structures, which are completely different in the members of the two families. Solid-state IR data of the complexes are discussed in terms of their structural features. 1H NMR data for the diamagnetic Y(III) complexes provide strong evidence that the compounds decompose in DMSO by releasing the coordinated salanH ligands. The solid complexes emit green light upon excitation at 360 nm (room temperature) or 405 nm (room temperature). The emission is ligand-based. The solid Pr(III), Nd(III), Sm(III), Er(III), and Yb(III) complexes of both families exhibit LnIII-centered emission in the near-IR region of the electromagnetic spectrum, but there is probably no efficient salanH→LnIII energy transfer responsible for this emission. Detailed magnetic studies reveal that complexes 7·MeCN_Dy, 17_Tb and 18_Dy show field-induced slow magnetic relaxation while complex [Tb(NO3)3(salanH)2(H2O)]·MeCN (6·MeCN_Tb) does not display such properties. The values of the effective energy barrier for magnetization reversal are 13.1 cm−1 for 7·MeCN_Dy, 14.8 cm−1 for 17_Tb, and 31.0 cm−1 for 18_Dy. The enhanced/improved properties of 17_Tb and 18_Dy, compared to those of 6_Tb and 7_Dy, have been correlated with the different supramolecular structural features of the two families. The molecules [Ln(NO3)3(salanH)2(MeOH)] of complexes 17_Tb and 18_Dy are by far better isolated (allowing for better slow magnetic relaxation properties) than the molecules [Ln(NO3)3(salanH)2(H2O)] in 6·MeCN_Tb and 7·MeCN_Dy. The perspectives of the present initial studies in the Ln(III)/salanH chemistry are discussed.

Synthesis, structures and spectroscopy of three new lanthanide β-diketonate complexes with 4,4′-dimethyl-2,2′-bipyridine. Near-infrared electroluminescence of ytterbium(III) complex in OLED

Three new lanthanide(III) β-diketonate complexes [Ln(btfa)3(4,4′-dmbpy)] (Ln = Yb(III), Gd(III) and Nd(III); btfa = anionic 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized and their characterization, including elemental analysis, FTIR spectroscopy and thermal analysis (TG/DTA), is reported. The crystal description based on powder X-ray diffraction reveals that Gd(III) and Yb(III) compounds are isostructural and that lanthanide ion is eight-coordinated by oxygen and nitrogen atoms to give new tris- β-diketonates [Ln(btfa)3(4,4′-dmbpy)]. The cell parameters of Nd(III) complex are close to Gd(III) and Yb(III) ones. Phosphorescence data of Gd(III) complex shows that the triplet states (T1) of the ligands have higher energy than the emitting states of Yb(III) and Nd(III), indicating the possibility of intramolecular energy transfer to these metal ions, which exhibit near-infrared (NIR) emission. We have used the Yb(III) complex as an emitting layer (EML) in a near infrared organic light emitting diode (NIR-OLED) with the structure: CuPc(15 nm)/XD-03(40 nm)/Yb(60 nm)/BCP(15 nm)/Alq3(10 nm)/Al(120 nm). OLEDs exhibit both visible electroluminescence and a NIR electroluminescence at 980 nm from the 2F5/2 → 2F7/2 transition of the Yb(III).

The new nir-emitting compounds based on β-dicarbonyl ligands

The Nd(III), Er(III) and Yb(III) complexes with allyl-3-oxobutanoate (allyl acetoacetate), 2-methyl-5-phenyl-1-penten-dione-3,5 (methacrylacetophenone) and their phenanthroline adducts were synthesized. Metallopolymers were obtained by radical polymerization. In all complexes β-dicarbonyl ligands are coordinated to central ions in a bidentate-cyclic mode. Thermal stability was shown to be higher for metallopolymers than for monomeric complexes. It was found that the displacement of water from the inner coordination environment of the Ln(III) ion and polymerization cause only minor deformation of the coordination polyhedrons, which all have non-cubic symmetry. The relative luminescence intensity of the complexes increases in the LnL3⋅2H2O < [LnL3]n < LnL3⋅Phen series. Among all studied lanthanides erbium compounds have the lowest luminescence intensity.

Near infrared electroluminescence polymeric systems containing β-diketones and lanthanides as emitters for organic light-emitting diodes

Nd(III), Er(III), and Yb(III) complexes with allyl-3-oxobutanoate (allyl acetoacetate) and their phenanthroline adducts as mixed ligand complexes (MLC) are synthesized. The polycomplexes on their basis and copolymers with methyl methacrylate in a ratio of 5:95 are obtained by the free-radical polymerization. The results of studies have shown that the configuration of the chelate unit is unchanged during the polymerization. By the luminescent spectroscopy, we have established that the luminescence intensity of MLC is considerably higher than for monoligand complexes due to the absence of water molecules in the coordination environment of Ln (III). The relative intensity of luminescent copolymers with methyl methacrylate on the MLC basis is significantly higher than that of the corresponding homopolymers, but lower than for mixed metal alloy complexes.

Modulation of the Prototropic Exchange Rate in pH‐Responsive Yb‐HPDO3A Derivatives as ParaCEST Agents

AbstractThe aim of this work was to design new pH‐sensitive paramagnetic chemical exchange saturation transfer (paraCEST) agents with a more acidic pH readout window with respect to the Yb complex of the 10‐(2‐hydroxypropyl)‐1,4,7,10‐ tetraazacyclododecane‐1,4,7‐triacetic acid (HPDO3A). In particular, three HPDO3A derivatives have been synthesized by substituting the methyl group on the 2‐hydroxypropyl arm with the electron withdrawing substituents –CF3, –CH2NH2 and –CH2OH. The Yb complexes have been characterized in terms of i) number and relative abundance of isomers present and, ii) pH sensitivity range in CEST applications. The influence of the introduced substituents on the –OH proton acidity and kex has been investigated and the new agents have been compared with the parent Yb‐HPDO3A. All complexes showed an increased acidity and an enhanced exchange rate of the –OH proton. As a consequence, the pH‐CEST sensitivity has been shifted to more acidic values. Eventually, the –CH2OH bearing derivative has been tested to assess the intra‐endosomal pH which is too acidic to be determined with Yb‐HPDO3A.

Near-Infrared Photoluminescence and Reversible Trans-to-Cis Photoisomerization of Mononuclear and Binuclear Ytterbium(III) Complexes Functionalized by Azobenzene Groups.

Two mononuclear and one binuclear ytterbium complexes with dual near-infrared (NIR) photoluminescence and reversible trans-to-cis photoisomerization functions were synthesized and characterized. The central ytterbium(III) ion coordinates with two β-diketonate (4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfd)) ligands and one deprotonated azobenzene-containing tetradentate ligand [(E)-4-(phenyldiazenyl)-N,N-bis(pyridin-2-ylmethyl) benzohydrazide (HL), (E)-4-((4-(dimethylamino)phenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl)benzohydrazide (HNL), or (E)-4,4′-N′,N′-bis(pyridin-2-ylmethyl)benzohydrazide azobenzene (H2DL)] to form a neutral ternary complex ([Yb(tfd)2L], [Yb(tfd)2(NL)], or [Yb2(tfd)4(DL)], respectively), where the ytterbium(III) ion is eight-coordinated to N3O5 donor sets. X-ray crystallographic analysis shows that all three complexes form a trigonal dodecahedron geometry with similar −N=N– distances that are slightly longer than those of the pure azobenzene-containing ligands. The NIR luminescence properties of the Yb(III) complexes were determined at a wavelength of about 980 nm with quantum yields in the range of 0.4–0.6% in ethanol and acetonitrile solutions at room temperature, and trans-to-cis photoisomerization was determined with the quantum yields (Φt→c = 10–2) at the same level as their pure ligands. The trans-to-cis photoisomerization rates of the complexes (10–4 s–1) are slightly higher than those of the pure ligands and similar to azobenzene (10–5 to 10–4 s–1). From time-dependent density functional theory calculations of the energy levels of the first excited triplet states of the ligands, the energies of the lowest excited triplet states of all of the ligands are higher than the resonance level of Yb3+ (2F5/2, 1.2722 eV). We suggest that these azo-containing ligands may participate in energy transfer to the ytterbium ion, in addition to the main “antenna effect” ligand tfd. This is the first report of azobenzene group-functionalized ytterbium complexes with dual NIR luminescence and photoisomerization properties, indicating that azobenzene-containing lanthanide(III) complexes have potential applications as dual function materials in biological systems.

Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines.

A series of polynuclear assemblies based on ligand L (1,4,7-tris[hydrogen (6-methylpyridin-2-yl)phosphonate]-1,4,7-triazacyclononane) has been developed. The coordination properties of ligand L with LnIII (Ln = La, Eu, Tb, Yb, Lu) have been studied in water (pH = 7.0) and in D2O (pD = 7.0) by UV-absorption spectrometry, spectrofluorimetry, 1H and 31P NMR, DOSY, ESI-mass spectrometry, and X-ray diffraction. This nonadentate ligand forms highly stable mononuclear complexes in water and provides a very efficient shielding of the Ln cations, as emphasized by the very good luminescence properties of the Yb complex in D2O, especially regarding its lifetime (τD2O = 10.2 μs) and quantum yield (ϕD2O = 0.42%). In the presence of excess LnIII cation, polynuclar complexes of [(LnL)2Ln x] stoichiometry (x = 1 and x = 2) are observed in solution. In the solid state, a dinuclear complex of La could be isolated and structurally characterized by X-ray diffraction, unraveling the presence of strong hydrogen bonding interactions between a La(H2O)93+ cation and the [LaL]3- complex.

Clinical Experience of Luminescent Diagnostics of Precancerous Diseases and Cervical Cancer

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Trivalent Rare-Earth-Metal Bis(trimethylsilyl)amide Halide Complexes by Targeted Oxidations.

In contrast to previously applied salt metathesis protocols the targeted rare-earth-metal compounds Ln[N(SiMe3)2]2(halogenido) were accessed by oxidation of Ln(II) silylamide precursors. Treatment of Sm[N(SiMe3)3]2(thf)2 with 0.5 equiv of C2Cl6 or 0.25 equiv of TeBr4 in thf and crystallization thereof gave [Sm{N(SiMe3)2}2(μ-X)(thf)]2 (X = Cl, Br). A similar reaction/crystallization procedure performed with 0.5 equiv of 1,2-diiodoethane gave monomeric Sm[N(SiMe3)2]2I(thf)2. Switching to Yb[N(SiMe3)2]2(thf)2, the aforementioned oxidants generated monomeric five-coordinate complexes Yb[N(SiMe3)2]2X(thf)2 (X = Cl, Br, I). The reaction of Eu[N(SiMe3)2]2(thf)2 with 0.5 equiv of C2Cl6 in thf yielded the separated ion pair [Eu{N(SiMe3)2}3Cl][(thf)5Eu(μ-Cl)2Eu(thf)5]. Performing the chlorination in n-hexane led to oxidation followed by rapid disproportionation into EuCl3(thf) x and Eu[N(SiMe3)2]3. The bromination reaction did not afford crystalline material, while the iodination gave crystals of divalent EuI2(thf)5. Use of trityl chloride (Ph3CCl) as the oxidant in thf accomplished the Eu(III) species [Eu{N(SiMe3)2}2(μ-Cl)(thf)]2. In situ oxidation of putative [Tm{N(SiMe3)2}2(thf) x] using 0.5 equiv of C2Cl6 in thf followed by crystallization from n-hexane led to the formation of a mixture of [Tm{N(SiMe3)2}2(μ-Cl)(thf)]2 and Tm[N(SiMe3)2]3. Switching the oxidant to 0.5 equiv of 1,2-diiodoethane and crystallizing from thf repeatedly afforded the bis-halogenated complex Tm[N(SiMe3)2]I2(thf)3.

Photoresponsive hydrogels with high wavelength selectivity for near-infrared light

Three rare earth organic complexes of Yb(TTA)2AAPhen, Nd(TTA)2AAPhen and Sm(TTA)2AAPhen with reactive ligands of acrylic acid (AA) were incorporated separately into poly(N-isopropylacrylamide) (PNIPAM) via in-situ free radical copolymerization. The synthesized three hydrogels with distinct dangling functional groups presented characteristic absorption peaks in near-infrared (NIR) light region and highly selective photothermal effects upon the illuminations of NIR light at 980 (Yb), 808 (Nd), and 1064 nm (Sm), respectively. Efficient volume contractions were merely achieved using the corresponding appropriate NIR light. The applications of photoresponsive hydrogels with high wavelength selectivity in microfluidic devices, controlled release carriers and soft actuators were explored.

Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand.

The synthesis of 4f n Ln3+ complexes of the tris(aryloxide) mesitylene ligand, ((Ad,MeArO)3mes)3-, with Ln = La, Ce, Pr, Sm, and Yb, and their reduction with potassium have revealed that this ligand system can be redox active with some metals. Protonolysis of [Ln(N(SiMe3)2)3] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) (Ad,MeArOH)3mes yielded the Ln3+ complexes [((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4f n complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln2+ ions with traditional 4f n+1 electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln3+ ions and ((Ad,MeArO)3mes)4- ligands. Structural comparisons of the [((Ad,MeArO)3mes)Ln] and [((Ad,MeOAr)3mes)Ln]1- complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.

Amido Ca and Yb(II) Complexes Coordinated by Amidine-Amidopyridinate Ligands for Catalytic Intermolecular Olefin Hydrophosphination.

A series of amido Ca and Yb(II) complexes LM[N(SiMe3)2](THF) (1Yb, 1-4Ca) coordinated by amidine-amidopyridinate ligands L1-4 were synthesized via a transamination reaction between proligands L1-4H and bisamido complexes M[N(SiMe3)2]2(THF)2 (M = Yb, Ca). The reactions of Yb[N(SiMe3)2]2(THF)2 with proligands L2H-L4H containing CF3 and C6H4F fragments do not allow for preparing the target Yb(II) complexes, while the Ca analogues were synthesized in good yields. Complexes 1Yb and 1-4Ca were evaluated as precatalysts for hydrophosphination of styrene, p-substituted styrenes, α-Me-styrene, and 2,3-dimethylbutadiene with various primary and secondary phosphines (PhPH2, 2,4,6-Me3C6H2PH2, 2-C5NH4PH2, Ph2PH, Cy2PH). Complexes 1Yb, 1-4Ca performed high catalytic activities in styrene hydrophosphination with PhPH2 and Ph2PH and demonstrated high regioselectivity affording exclusively the anti-Markovnikov addition products. For primary PhPH2 the reactions (1:1 molar ratio of substrates) catalyzed by 1Yb, 1Ca, and 2Ca proved to be highly chemoselective affording the secondary phosphine Ph(PhCH2CH2)PH; however, complexes 3Ca and 4Ca led to the formation of both secondary and tertiary phosphines in 80:20 and 86:14 ratios. Styrene hydrophosphinations with 2,4,6-Me3C6H2PH2 and 2-pyridylphosphine for all complexes 1Yb and 1-4Ca proceeded much more slowly compared to PhPH2. Addition of 2-C5NH4PH2 to styrene catalyzed by complex 1Yb turned out to be non-regioselective and led to the formation of a mixture of Markovnikov and anti-Markovnikov addition products, while all Ca complexes enabled regioselective anti-Markovnikov addition. Complexes 1Ca and 1Yb containing catalytic centers featuring similar ionic radii performed different catalytic activity: the ytterbium analogue proved to be a more active catalyst for intermolecular hydrophosphination of styrene with Cy2PH, 2-C5NH4PH2, and PhPH2, but less active with sterically demanding 2,4,6-Me3C6H2PH2. Styrenes containing in p-position electron-donating groups (Me, tBu, OMe) performed with noticeably lower rates in the reactions with PhPH2 compared to styrene. Complexes 1Yb, 1Ca, 2Ca, 3Ca, and 4Ca enabled addition of PhPH2 toward the double C═C bond of α-Me-styrene, and the reaction rate for this substrate is noticeably lower; however quantitative conversions were reached in ∼40 h. Complexes 1Ca and 2Ca promoted 1,2-addition of PhPH2 to 2,3-dimethyl butadiene with excellent regio- and chemoselectivity to afford linear secondary phosphines. Hydrophosphination of inert 1-nonene with Ph2PH with 40% conversion becomes possible due to the application of complex 2Ca (40 h, 70 °C). The rate law for the hydrophosphination of styrene with Ph2PH catalyzed by 1Ca was found to agree with the idealized equation: v = k[styrene]1[1Ca]1.

Primary aminomethyl derivatives of kaempferol: hydrogen bond-assisted synthesis, anticancer activity and spectral properties.

A series of primary aminomethyl derivatives of kaempferol were synthesized by a combination strategy involving two steps of the Mannich reaction and SN2 nucleophilic substitution. The structures of the products show that the preferential aminomethylations are in the position C-6 or C-8 of the A-ring of kaempferol, especially the latter. Interestingly, the experimental data indicate that the intermolecular hydrogen bonding plays a key role in the formation of primary aminomethyl products of kaempferol. The formation of appropriate hydrogen bonds between strong nucleophilic amino acids and phenol is essential for the smooth reaction of the SN2 nucleophilic substitution. The SN2 mechanism hypothesis involving a hydrogen bond-assisted process was also supported by the density functional theory (DFT) analysis. An antiproliferative test of synthetic compounds shows the moderate to potent cytotoxic activity against three human cancer cell lines (HeLa, HCC1954, and SK-OV-3) by the CCK-8 assay. Compound 4e shows selective antiproliferative activity against HeLa cells with a low IC50 value (4.27 μm) and is worthy of further development. Another interesting result is that the maximum emission bands for most metal complexes are located at about 480 nm, but the ones for Tm and Yb complexes appear at about 533 nm.

Seven-coordinate lanthanide complexes with a tripodal redox active ligand: structural, electrochemical and spectroscopic investigations.

The tripodal ligand TREN-(3,5-di-tert-butylsalicylidene)3 (H3L) was synthesized and its tris(phenolato) lanthanide complexes L-Ln (Ln = NdIII, EuIII, TbIII, GdIII, ErIII, YbIII and LuIII) were prepared. The X-Ray crystal structures confirm that each metal ion resides in a similar monocapped octahedral geometry, excluding water molecules from the coordination sphere. The coordination bond distances are in agreement with the lanthanide contraction, with Ln-O bond lengths in the range 2.139-2.216 Å. The complexes show three reversible monoelectronic oxidation waves, which are assigned to the successive oxidation of the phenolate moieties to phenoxyl radicals. The L-Nd complex is the easiest to oxidize, with E = 0.11, E = 0.21 and E = 0.34 V vs. Fc+/Fc, due to the larger size of the lanthanide ion. The ΔE1/2 value (ΔE1/2 = E-E) is correlated to the lanthanide radius, with values of 0.10 V for L-Nd and 0.22 V for L-Lu. The monoradical species were persistent in solution, allowing for their characterisation. All exhibit a distinct absorption band at around 445 nm due to the phenoxyl π-π* transitions. The EPR spectrum of L-Lu+ consists of a single resonance at giso = 1.999, confirming the radical nature of the oxidized product. Most of the other complexes (L-Gd, L-Er, L-Yb) show a quenching of the LnIII-based resonances upon oxidation, indicative of magnetic interactions between the metal and the radical spins. The L-Ln (L = Nd, Er, Yb) complexes exhibit a metal-based luminescence upon excitation of the ligand. A significant quenching of the luminescence was observed upon radical formation: 92%, 83% and 79% respectively for L-Nd+, L-Er+ and L-Yb+.

Exquisite sensitivity of the ligand field to solvation and donor polarisability in coordinatively saturated lanthanide complexes

Crystallographic, emission and NMR studies of a series of C3-symmetric, nine-coordinate substituted pyridyl triazacyclononane Yb(iii) and Eu(iii) complexes reveal the impact of local solvation and ligand dipolar polarisability on ligand field strength, leading to dramatic variations in pseudocontact NMR shifts and emission spectral profiles, giving new guidance for responsive NMR and spectral probe design.