Seeking Brightness in Molecular Erbium-Based Light Upconversion.

Whereas dye-sensitized lanthanide-doped nanoparticles represent an unquestionable advance for pushing linear near-infrared (NIR) to visible-light upconversion within the frame of applications, analogous improvements are difficult to mimic for related but intramolecular processes induced at the molecular level in coordination complexes. Major difficulties arise from the cationic nature of the target cyanine-containing sensitizers (S), which drastically limits their thermodynamic affinities for catching the lanthanide activators (A) required for performing linear light upconversion. In this context, the rare previous design of stable dye-containing molecular SA light-upconverters required large S···A distances at the cost of the operation of only poorly efficient intramolecular S → A energy transfers and global sensitization. With the synthesis of the compact ligand [L2]+, we exploit here the benefit of using a single sulfur connector between the dye and the binding unit for counterbalancing the drastic electrostatic penalty which is expected to prevent metal complexation. Quantitative amounts of nine-coordinate [L2Er(hfac)3]+ molecular adducts could be finally prepared in solution at millimolar concentrations, while the S···A distance has been reduced by 40% to reach circa 0.7 nm. Detailed photophysical studies demonstrate the operation of a three times improved energy transfer upconversion (ETU) mechanism for molecular [L2Er(hfac)3]+ in acetonitrile at room temperature, thanks to the boosted heavy atom effect operating in the close cyanine/Er pair. NIR excitation at 801 nm can thus be upconverted into visible light (525-545 nm) with an unprecedented brightness of Bup(801 nm) = 2.0(1) × 10-3 M-1·cm-1 for a molecular lanthanide complex.

Metal-Based Linear Light Upconversion Implemented in Molecular Complexes: Challenges and Perspectives.

The piling up of low-energy photons to produce light beams of higher energies while exploiting the nonlinear optical response of matter was conceived theoretically around 1930 and demonstrated 30 years later with the help of the first coherent ruby lasers. The vanishingly small efficacy of the associated light-upconversion process was rapidly overcome by the implementation of powerful successive absorptions of two photons using linear optics in materials that possess real intermediate excited states working as relays. In these systems, the key point requires a favorable competition between the rate constant of the excited-state absorption (ESA) and the relaxation rate of the intermediate excited state, the lifetime of which should be thus maximized. Chemists and physicists therefore selected long-lived intermediate excited states found (i) in trivalent lanthanide cations doped into ionic solids or into nanoparticles (2S+1LJ spectroscopic levels) or (ii) in polyaromatic molecules (triplet states) as the logical activators for designing light upconverters using linear optics. Their global efficiency has been stepwise optimized during the past five decades by using indirect intermolecular sensitization mechanisms (energy transfer upconversion = ETU) combined with large absorption cross sections.The induction of light-upconversion operating in a single discrete entity at the molecular level is limited to metal-based units and remained a challenge for a long time because coordination complexes possess high-frequency oscillators incompatible with the existence of (i) scales of accessible excited relays with long lifetimes and (ii) final high-energy emissive levels with noticeable intrinsic quantum yields. In contrast to intermolecular energy transfer processes operating in metal-based doped solids, which require statistical models, the combination of sensitizers and activators within the same molecule limits energy transfers to easily tunable intramolecular processes with first-order kinetic rate constants. Their successful programming in a trinuclear CrErCr complex in 2011 led to the first detectable near-infrared to green light upconversion induced in a molecular unit under reasonable excitation intensity. The subsequent progress in the modeling and understanding of the key factors controlling metal-based light upconversion operating in molecular complexes led to a burst of various designs exploiting different mechanisms, excited-state absorption (ESA), energy transfer upconversion (ETU), cooperative luminescence (CL), and cooperative upconversion (CU), which are discussed in this Account.

Ligand-Sensitized Near-Infrared to Visible Linear Light Upconversion in a Discrete Molecular Erbium Complex.

While the low-absorption cross section of lanthanide-based upconversion systems, in which the trivalent lanthanides (Ln3+) are responsible for converting low- to high-energy photons, has restricted their application to intense incident light, the emergence of a cascade sensitization through an organic dye antenna capable of broadly harvesting near-infrared (NIR) light in upconversion nanoparticles opened new horizons in the field. With the aim of pushing molecular upconversion within the range of practical applications, we show herein how the incorporation of an NIR organic dye antenna into the ligand scaffold of a mononuclear erbium coordination complex boosts the upconversion brightness of the molecule to such an extent that a low-power (0.7 W·cm-2) NIR laser excitation of [L6Er(hfa)3]+ (hfa = hexafluoroacetylacetonate) at 801 nm results in a measurable visible upconverted signal in a dilute solution (5 × 10-4 M) at room temperature. Connecting the NIR dye antenna to the Er3+ activator in a single discrete molecule cures the inherent low-efficient metal-based excited-state absorption mechanism with a powerful indirect sensitization via an energy transfer upconversion, which drastically improves the molecular-based upconverted Er3+-centered visible emission.

Molecular light-upconversion: we have had a problem! When excited state absorption (ESA) overcomes energy transfer upconversion (ETU) in Cr(III)/Er(III) complexes.

Nine-coordinate [ErN9] or [ErN3O6] chromophores found in triple helical [Er(L)3]3+ complexes (L corresponds to 2,2',6',2''-terpyridine (tpy), 2,6-(bisbenzimidazol-2-yl)pyridine (bzimpy), 2,6-diethylcarboxypyridine (dpa-ester) or 2,6-diethylcarboxamidopyridine (dpa-diamide) derivatives), [Er(dpa)3]3- (dpa is the 2,6-dipicolinate dianion) and [GaErGa(bpb-bzimpy)3]9+ (bpb-bzimpy is 2,6-bis((pyridin-2-benzimidazol-5-yl)methyl-(benzimidazol-2-yl))pyridine) exhibit NIR (excitation at 801 nm) into visible (emission at 542 nm) linear light upconversion processes in acetonitrile at room temperature. The associated quantum yields 5.5(6) × 10-11 ≤ φuptot(ESA) ≤ 1.7(2) × 10-9 appear to be 1-3 orders of magnitude larger than those predicted by the accepted single-center excited-state absorption mechanism (ESA). Switching to the alternative energy transfer upconversion mechanism (ETU), which operates in multi-centers [CrErCr(bpb-bzimpy)3]9+, leads to an improved quantum yield of φuptot(ETU) = 5.8(6) × 10-8, but also to an even larger discrepancy by 4-6 orders of magnitude when compared with theoretical models. All photophysical studies point to Er(4I13/2) as being the only available 'long-lived' (1.8 ≤ τ ≤ 6.3 µs) and emissive excited state, which works as an intermediate relay for absorbing the second photon, but with an unexpected large cross-section for an intrashell 4f → 4f electronic transition. With this in mind, the ETU mechanism, thought to optimize upconversion via intermetallic Cr → Er communication in [CrErCr(bpb-bzimpy)3]9+, is indeed not crucial and the boosted associated upconversion quantum yield is indebted to the dominant contribution of the single-center erbium ESA process. This curious phenomenon is responsible for the successful implementation of light upconversion in molecular coordination complexes under reasonable light power intensities, which paves the way for applications in medicine and biology. Its origin could be linked with the presence of metal-ligand bonding.

Deciphering and quantifying linear light upconversion in molecular erbium complexes.

Single-center light upconversion corresponds to the piling up of low-energy photons via successive linear absorptions: a phenomenon commonly observed in lanthanide-doped low-phonon ionic solids or nanoparticles. Its ultimate miniaturization in molecular complexes opens challenging perspectives in terms of improved reproducibility, chemical control and optical programming. However, high-energy vibrations inherent in coordination complexes severely limit the efficiency of successive excited-state absorptions (ESAs) responsible for the gain in photon energy. By carefully wrapping three polyaromatic ligand strands around trivalent erbium, we managed to induce low-power room temperature near-infrared (λ exc = 801 nm or 966 nm) to visible green (λ em = 522 nm and 545 nm) light upconversion within mononuclear coordination complexes [Er(Lk )3]3+ operating either in the solid state or in non-deuterated solution. The calculated upconversion quantum yields set the zero-level of an elemental erbium-centered molecular ESA mechanism, a value which favorably compares with cooperative upconversion (CU) previously implemented in sophisticated multisite Yb2Tb supramolecular assemblies. The various dependences of the upconverted emission on the incident excitation power imply different mechanisms, which can be tuned by molecular design.

Room-Temperature Linear Light Upconversion in a Mononuclear Erbium Molecular Complex.

To date, the piling up of successive photons of low energies (near infrared; NIR) using a single lanthanide center and linear optics to ultimately produce upconverted visible emission was restricted to low-phonon solid materials and nanoparticles. Now we show that the tight helical wrapping of three terdentate N-donor ligands around a single nine-coordinate trivalent erbium cation provides favorable conditions for a mononuclear molecular complex to exhibit unprecedented related upconverted emission. Low power NIR laser excitations into the metal-centered transitions Er(4 I11/2 ←4 I15/2 ) at 801 nm or Er(4 I13/2 ←4 I15/2 ) at 966 nm result in upconverted blue-green emissions, where two or three photons respectively are successively absorbed by a molecular lanthanide complex possessing high-energy vibrations.

Thermodynamic Programming of Erbium(III) Coordination Complexes for Dual Visible/Near-Infrared Luminescence.

Intrigued by the unexpected room-temperature dual visible/near-infrared (NIR) luminescence observed for fast-relaxing erbium complexes embedded in triple-stranded helicates, in this contribution, we explore a series of six tridentate N-donor receptors L4-L9 with variable aromaticities and alkyl substituents to extricate the stereoelectronic features responsible for such scarce optical signatures. Detailed solid-state (X-ray diffraction, differential scanning calorimetry, optical spectroscopy) and solution (speciations and thermodynamic stabilities, spectrophotometry, NMR and optical spectroscopy) studies of mononuclear unsaturated [Er(Lk)2 ]3+ and saturated triple-helical [Er(Lk)3 ]3+ model complexes reveal that the stereoelectronic changes induced by the organic ligands affect inter- and intramolecular interactions to such an extent that 1) melting temperatures in solids, 2) the affinity for trivalent erbium in solution, and 3) optical properties in luminescent complexes can be rationally varied and controlled. With this toolkit in hand, mononuclear erbium complexes with low stabilities displaying only NIR emission can be transformed into molecular-based dual Er-centered visible/NIR emitters operating at room temperature in both solid and solution states.

Taming Lanthanide-Centered Upconversion at the Molecular Level.

Considered at the beginning of the 21th century as being incompatible with the presence of closely bound high-energy oscillators, lanthanide-centered superexcitation, which is the raising of an already excited electron to an even higher level by excited-state energy absorption, is therefore a very active topic strictly limited to the statistical doping of low-phonon bulk solids and nanoparticles. We show here that molecular lanthanide-containing coordination complexes may be judiciously tuned to overcome these limitations and to induce near-infrared (NIR)-to-visible (VIS)-light upconversion via the successive absorption of two low-energy photons using linear-optical responses. Whereas single-ion-centered excited-state absorption mechanisms remain difficult to implement in lanthanide complexes, the skillful design of intramolecular intermetallic energy-transfer processes operating in multimetallic architectures is at the origin of the recent programming of erbium-centered molecular upconversion.