Two-Photon Circularly Polarized Luminescence of Chiral Eu Complexes.

We report the synthesis of chiral lanthanide complexes with extended π conjugation for efficient circularly polarized luminescence (CPL) via two-photon excitation (2PE). The pyridine bis-oxazoline (PyBox) core provides the chiral Ln3+ environment, while the extension of the conjugated backbone through the pyridine 4-position with a phenylacetylene unit increases the two-photon absorption cross section. This work presents an important step toward the development of chiral systems displaying enhanced nonlinear optical properties, with potential applications in imaging and sensing, as well as in photodynamic therapy due to the selective excitation of molecules within a specific focal volume.

Circularly Polarized Luminescence from New Heteroleptic Eu(III) and Tb(III) Complexes.

The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S1 and T1 ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (ηsens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕovl = 55%; ηsens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of glum (0.26) and a good quantum yield (26%) were measured.

NIR-Circularly Polarized Luminescence from Chiral Complexes of Lanthanides and d-Metals.

In recent years, circularly polarized luminescence (CPL) has witnessed a renaissance, due to the increased popularity of CPL as a spectroscopic technique and greater accessibility to instrumentation. New efficient CPL emitters have been designed and many applications, ranging from electronic devices to microscopy have been proposed. Most examples of CPL are within the visible range, while few cases of near infrared (NIR) CPL active complexes are available. NIR-CPL compounds may have applications in the telecommunication industry, electronic devices and bioassays. In the following, we shall give an overview of the recent developments allowing for the measurements of NIR-CPL, and describe the chiroptical properties of metal complexes which achieve this feat.

Efficient 1400-1600†nm Circularly Polarized Luminescence from a Tuned Chiral Erbium Complex.

Novel chiral Er complexes based on both enantiomers of extended i PrPyBox (2,6-Bis[4-isopropyl-4,5-dihydrooxazol-2-yl)]pyridine) show strong near-infrared circularly polarized luminescence (CPL) within the 1400 to 1600 nm spectral region under 450 nm irradiation. CPL activity in this region, despite being particularly rare, would open the way to potential applications in the domain, e.g., of fiber-optic telecommunications and free-space long-distance optical communications employing circularly polarized light. Moreover, the long wavelength excitation is advantageous for applications in the field of (circularly polarized) microscopy and bioimaging.

Near Infared Circularly Polarized Luminescence From Water Stable Organic Nanoparticles Containing a Chiral Yb(III) Complex.

We report the first example of very efficient NIR Circularly Polarized Luminescence (CPL) (around 970 nm) in water, obtained thanks to the combined use of a chiral Yb complex and of poly lactic-co-glycolic acid (PLGA) nanoparticles. [YbL(tta)2 ]CH3 COO (L=N, N'-bis(2-pyridylmethylidene)-1,2-(R,R+S,S) cyclohexanediamine and tta=2-thenoyltrifluoroacetonate) shows good CPL in organic solvents, because the tta ligands efficiently sensitize Yb NIR luminescence and the readily prepared chiral ligand L endows the complex with the necessary dissymmetry. PLGA nanoparticles incorporate the complex and protect the metal ion from the intrusion of solvent molecules, while ensuring biocompatibility, water solubility and stability to the complex. Hydrophilic NIR-CPL optical probes can find applications in the field of NIR-CPL bio-assays.

Remarkable near-infrared chiroptical properties of chiral Yb, Tm and Er complexes.

We carried out a study of absorption (CD) and emission (CPL) chiroptical properties in the NIR region of two sets of Yb, Tm and Er complexes. The two complexes include a D3 symmetric, [TMG-H+]3Ln(BINOLate)3 (Ln = Yb, Tm, Er; TMG = 1,1,3,3-tetramethylguanidine; BINOLate = 1,1'-bi-2-naphtholate), and a tetrakis, C4 symmetric, CsLn(hfbc)4 (Ln = Yb, Tm, Er; hfbc = 3-heptafluorobutylyrylcamphorate). The lanthanides studied gave access to three discrete energy domains, Yb (900-1040 nm), Tm (1180-1240 nm) and Er (1430-1600 nm) in which the chiroptical activity was assessed using gabs (and glum for Yb complexes). Exceptionally high discrimination between left and right circularly polarised light was observed, with values up to almost the theoretical maximum (±2).

Powering Electronic Devices from Salt Gradients in AA-Battery-Sized Stacks of Hydrogel-Infused Paper.

Strongly electric fish use gradients of ions within their bodies to generate stunning external electrical discharges; the most powerful of these organisms, the Atlantic torpedo ray, can produce pulses of over 1 kW from its electric organs. Despite extensive study of this phenomenon in nature, the development of artificial power generation schemes based on ion gradients for portable, wearable, or implantable human use has remained out of reach. Previously, an artificial electric organ inspired by the electric eel demonstrated that electricity generated from ion gradients within stacked hydrogels can exceed 100 V. The current of this power source, however, was too low to power standard electronics. Here, an artificial electric organ inspired by the unique morphologies of torpedo rays for maximal current output is introduced. This power source uses a hybrid material of hydrogel-infused paper to create, organize, and reconfigure stacks of thin, arbitrarily large gel films in series and in parallel. The resulting increase in electrical power by almost two orders of magnitude compared to the original eel-inspired design makes it possible to power electronic devices and establishes that biology's mechanism of generating significant electrical power can now be realized from benign and soft materials in a portable size.