Unravelling Kinetics of Intramolecular NdIII → FeII Energy Transfer in Spin Crossover Single Molecules: Dotting the i's and Crossing the t's.

Compared with the ripple of visible EuIII-based emission intensity induced by appended [FeIIN6] spin crossover (SCO) units, as detected in the triple-stranded [EuFe(L1)3]5+ helicate, the lanthanide-based luminescent detection of FeII spin-state equilibria could be improved significantly if the luminophore emission is shifted toward the near-infrared (NIR) domain. Replacing EuIII with NdIII in [NdFe(L1)3]5+ (i) maintains the favorable SCO properties in acetonitrile [critical temperature T1/2 = 322(2) K], (ii) saturates nonradiative vibrational relaxation processes in the 233-333 K range, and (iii) boosts the crucial intramolecular NdIII → FeII energy transfer rate processes, which are sensitive to the spin state of the FeII metallic center. Consequently, the steady-state NIR Nd(4F3/2 → 4IJ) emission of the luminophore is amplified and linearly correlated with the low-spin-[FeIIN6] and high-spin-[FeIIN6] mole fractions controlled by the SCO equilibrium. This paves the way for a straightforward and direct NIR luminescent reading/sensing of the FeII spin state in single molecules.

Taming 2,2'-biimidazole ligands in trivalent chromium complexes.

Complete or partial replacement of well-known five-membered chelating 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) ligands with analogous didentate 2,2'-biimidazole (H2biim) provides novel perspectives for exploiting the latter pH-tuneable bridging unit for connecting inert trivalent chromium with cationic partners. The most simple homoleptic complex [Cr(H2biim)3]3+ and its stepwise deprotonated analogues are only poorly soluble in most solvents and their characterization is limited to some solid-state structures, in which the pseudo-octahedral [CrN6] units are found to be intermolecularly connected via peripheral N-H⋯X hydrogen bonds. Moreover, the associated high-energy stretching N-H vibrations drastically quench the targeted near infrared (NIR) CrIII-based phosphorescence, which makes these homoleptic building blocks incompatible with the design of molecular-based luminescent assemblies. Restricting the number of bound 2,2'-biimidazole ligands to a single unit in the challenging heteroleptic [Cr(phen)2(Hxbiim)](1+x)+ (x = 2-0) complexes overcomes the latter limitations and allows (i) the synthesis and characterization of these [CrN6] chromophores in the solid state and in solution, (ii) the stepwise and controlled deprotonation of the bound 2,2'-biimidazole ligand and (iii) the implementation of Cr-centered phosphorescence with energies, lifetimes and quantum yields adapted for using the latter chromophores as sensitizers in promising 'complex-as-ligand' strategies.

Programming heterometallic 4f-4f' helicates under thermodynamic control: the circle is complete.

Three non-symmetrical segmental ligand strands L4 can be wrapped around a linear sequence of one Zn2+ and two trivalent lanthanide cations Ln3+ to give quantitatively directional [ZnLn2(L4)3]8+ triple-stranded helicates in the solid state and in solution. NMR speciations in CD3CN show negligible decomplexation at a millimolar concentration and the latter helicate can be thus safely considered as a preorganized C3-symmetrical HHH-[(L43Zn)(LnA)(2-n)(LnB)n]8+ platform in which the thermodynamic properties of (i) lanthanide permutation between the central N9 and the terminal N6O3 binding sites and (ii) exchange processes between homo- and heterolanthanide helicates are easy to access (Ln = La, Eu, Lu). Deviations from statistical distributions could be programmed by exploiting specific site recognition and intermetallic pair interactions. Considering the challenging La3+ : Eu3+ ionic pair, for which the sizes of the two cations differ by only 8%, a remarkable excess (70%) of the heterolanthanide is produced, together with a preference for the formation of the isomer where the largest lanthanum cation lies in the central N9 site ([(La)(Eu)] : [(Eu)(La)] = 9 : 1). This rare design and its rational programming pave the way for the preparation of directional light-converters and/or molecular Q-bits at the (supra)molecular level.

Tuning Selectivity and Stability in Heteroleptic Lanthanide Adducts by Ligand Design.

Terdentate ligands L10-L14 and their heteroleptic [LkLn(hfac)3] complexes (Ln = La, Eu, Gd, Er, or Y; H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) exhibit multifactorial correlations between the ligand's structural frameworks, including their level of preorganization and steric congestion and their affinities and selectivities for catching the trivalent lanthanide containers [Ln(hfac)3]. The polyaromatic ligand scaffolds could be stepwise modulated via lanthanide-template synthetic strategies, using intermolecular rhodium-catalyzed insertion reactions. The increasing level of preorganization along the L10 → L11 → L12 series leads to a duality in which larger thermodynamic formation constants with lanthanides in CD2Cl2 are accompanied by an unexpected decrease in the Ln-N affinities in the solid state, which could be assigned to a limited match between the lanthanide size and the enlarged preorganized cavities. On the contrary, a reduced stability is induced by the connection of additional methyl groups at position 1 of the benzimidazole moieties in L13 and L14, which is accompanied by an optimization of metal-nitrogen bond lengths. This study contributes to the rational design of highly stable neutral heteroleptic lanthanide ß-diketonate adducts that resist dissociation in solution, a prerequisite for photophysical applications using these highly luminescent systems at the molecular level.

Additional Insights into the Design of Cr(III) Phosphorescent Emitters Using 6-Membered Chelate Ring Bis(imidazolyl) Didentate Ligands.

The interest in Cr(III) complexes has been renewed over the past decades for building practical guidelines in the design of efficient earth-abundant phosphorescent near-infrared emitters. In that context, we report the first family of homoleptic tri(didentate) Cr(III) complexes [CrL3]3+ based on polyaromatic ligands inducing 6-membered chelate rings, namely, the bis(1-methylimidazol-2-yl)ketone (L = bik), bis(1-methylimidazol-2-yl)methane (L = bim), and bis(1-methylimidazol-2-yl)ethane (L = bie) ligands. The programmed close-to-perfect octahedral microsymmetry of {CrIIIN6} chromophores found in [Cr(bik)3](OTf)3 (1), [Cr(bim)3](OTf)3 (2), and [Cr(bie)3](BF4)3 (3) ensures a ligand-field strength large enough to induce intense and long-lived Cr-based phosphorescence. Impressive excited-state lifetimes (5.0-8.2 ms) were obtained at low temperatures for the [Cr(L)3]3+ series. Additionally, the photoluminescent quantum yield climbs to 0.8% for compound 1 in deaerated solutions. Moreover, the photophysical features of the three homoleptic complexes are barely influenced by the presence of dioxygen presumably because of the poor overlap between the Cr-based phosphorescence spectra (ca. 14100 cm-1) and the 1Σg+ ← 3Σg- transition in the absorption spectrum of dioxygen (13100 cm-1). The multiredox electrochemical pattern of 1 is evidenced by cyclic voltammetry as well as its strong photooxidant behavior. The pH sensitivity of 2 and 3 luminescence is discussed, along with the reactivity of their ß-diketiminate derivatives.

Detecting Fe(II) Spin-Crossover by Modulation of Appended Eu(III) Luminescence in a Single Molecule.

Multifunctionality in spin-crossover (SCO) devices is limited to macroscopic or nanoscopic materials because of the need for long-range effects for inducing favorable cooperativity, efficient energy migration processes, and detectable magnetization transfer. The difficult reproducibility, control, and rational design of doped materials offer some place to SCO processes, modulating the optical properties of neighboring luminescent probes in single molecules. We report here on the combination of a [FeN6] chromophore, the SCO temperature and absorption spectra of which have been tuned to induce unprecedented room-temperature modulation of Eu(III)-based line-like luminescence in the molecular triple-helical [EuFe(L2)3]5+ complex in solution.

Symmetry and Rigidity for Boosting Erbium-Based Molecular Light-Upconversion in Solution.

Previously limited to highly symmetrical homoleptic triple-helical complexes [Er(Lk)3 ]3+ , where Lk are polyaromatic tridentate ligands, single-center molecular-based upconversion using linear optics and exploiting the excited-state absorption mechanism (ESA) greatly benefits from the design of stable and low-symmetrical [LkEr(hfa)3 ] heteroleptic adducts (hfa- =hexafluoroacetylacetonate anion). Depending on (i) the extended π-electron delocalization, (ii) the flexibility and (iii) the heavy atom effect brought by the bound ligand Lk, the near-infrared (801 nm) to visible green (542 nm) upconversion quantum yield measured for [LkEr(hfa)3 ] in solution at room temperature can be boosted by up to three orders of magnitude.

Rational Loading of Linear Multi-Site Receptors with Functional Lanthanide Containers: The Missing Link between Oligomers and Polymers.

Although metal-containing organic polymers are becoming essential for modern applications in lighting, catalysis, and electronic devices, very little is known about their controlled metallic loading, which mainly limits their design to empirical mixing followed by characterization and often hampers rational developments. Focusing on the appealing optical and magnetic properties of 4f-block cations, the host-guest reactions leading to linear lanthanidopolymers already display some unexpected dependence of the binding-site affinities on the length of the organic polymer backbone: a drift usually, and erroneously, assigned to intersite cooperativity. Taking advantage of the parameters obtained for the stepwise thermodynamic loading of a series of rigid linear multi-tridentate organic receptors with increasing length, N = 1 (monomer L1), N = 2 (dimer L2), and N = 3 (trimer L3), with [Ln(hfa)3] containers in solution (Ln = trivalent lanthanide cations, hfa- = 1,1,1,5,5,5-hexafluoro-pentane-2,4-dione anion), it is demonstrated here that the site-binding model, based on the Potts-Ising approach, successfully predicts the binding properties of the novel soluble polymer P2N made up of nine successive binding units . An in-depth examination of the photophysical properties of these lanthanidopolymers shows impressive UV→vis downshifting quantum yields for the europium-based red luminescence, which can be modulated by the length of the polymeric chain.

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.

Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(ß-diketonate)3 ] Guests in Solution.

The concept of preorganization is famous in coordination chemistry for having transformed flexible bidentate 2,2'-bipyridine scaffolds into rigid 1,10-phenanthroline platforms. The resulting boosted affinities for d-block cations has successfully paved the way for the design of a wealth of functional complexes, devices and materials for analysis and optics. Its extension toward terdentate homologues adapted for the selective complexation of f-block cations with larger coordination numbers remains more overlooked. The resulting rigidification of 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine ligands (L1-L7) produces the highly preorganized and extended polyaromatic benzo[4',5']imidazo[1',2' : 1,2]pyrido[3,4-b]benzo[4,5]imidazo[1,2-h][1,7]naphthyridines (L8-L11) receptors, which offer some novel and rare opportunities for efficiently complexing trivalent lanthanides with polyaromatic soft terimine ligands. The crystal structures of the stable heteroleptic [LkLn(hfac)3 ] adducts (Lk=L1, L8, L9; Ln=La, Eu, Gd, Er, Yb, Y; H-hfac=1,1,1,5,5,5-hexafluoropentane-2,4-dione) show a drastic decrease in the Ln-N bond valences upon replacement of the flexible ligand L1 with its preorganized counterparts L8 and L9. This points to a limited match between the preorganized cavity and the entering [Ln(hfac)3 ] lanthanide containers. However, thermodynamic studies conducted in dichloromethane reach the opposite conclusion, with an improved affinity, by up to three orders of magnitude for catching Ln(hfac)3 when L1 is replaced by the preorganized L8-L9 receptors. The key to the enigma lies in the removal of the energy penalty which accompanies the formation of flexible [L1Ln(hfac)3 ] complexes in solution. This driving force overcomes the poor match between the preorganized terdentate N∩ N∩ N cavity in L8 and L9 and the size of trivalent lanthanides. As planned, the rigid, planar and extended π-conjugated system found in L8 and L9 shifts the ligand-centered absorption bands by about 5000 cm-1 toward lower energies, a crucial point if these stable [L8Ln(hfac)3 ] and [L9Ln(hfac)3 ] platforms have to be considered for the visible sensitization of luminescent lanthanides in metallopolymers.

Complex-as-Ligand Strategy as a Tool for the Design of a Binuclear Nonsymmetrical Chromium(III) Assembly: Near-Infrared Double Emission and Intramolecular Energy Transfer.

The chromium(III) polypyridyl complexes are appealing for their long-lived near-infrared (NIR) emission reaching the millisecond range and for the strong circularly polarized luminescence of their isolated enantiomers. However, harnessing those properties in functional polynuclear CrIII devices remains mainly inaccessible because of the lack of synthetic methods for their design and functionalization. Even the preparation and investigation of most basic nonsymmetrical CrIII dyads exhibiting directional intramolecular intermetallic energy transfer remain unexplored. Taking advantage of the inertness of heteroleptic chromium(III) polypyridyl building blocks, we herein adapt the "complex-as-ligand" strategy, largely used with precious 4d and 5d metals, for the preparation of a binuclear nonsymmetrical CrIII complex (3d metal). The resulting [(phen)2Cr(L)Cr(tpy)]6+ dyad shows dual long-lived NIR emission and a directional intermetallic energy transfer that is controlled by the specific arrangements of the different coordination spheres. This strategy opens a route for building predetermined polynuclear assemblies with this earth-abundant metal.

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α'-Diimine Ligands.

Invited for the cover of this issue are Davood Zare, Claude Piguet, Edwin C. Constable and co-workers at the University of Basel and the University of Geneva. The image depicts a [AgI L]+ intermediate about to catch a second α,α'-diimine ligand to form the stable [AgI L2 ]+ . Read the full text of the article at 10.1002/chem.202200912.

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α'-Diimine Ligands.

The allosteric positive cooperativity accompanying the formation of compact [CuI (α,α'-diimine)2 ]+ building blocks contributed to the historically efficient synthesis of metal-containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen-resistant [AgI (α,α'-diimine)2 ]+ units in modern entangled metallo-supramolecular assemblies, a related thermodynamic justification was absent. Solid-state structural characterizations show the successive formation of [AgI (α,α'-diimine)(CH3 CN)][X] and [AgI (α,α'-diimine)2 ][X] upon the stepwise reactions of α,α'-diimine=2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives with AgX (X=BF4 - , ClO4 - , PF6 - ). In room-temperature, 5-10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non-cooperative) binding of two successive bidentate ligands around AgI , a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6' positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)2 ]+ and [Ag(dmphen)2 ]+ , a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)2 ]+ further reinforces the positively cooperative process, while limiting the overall decrease in metal-ligand affinity.

Heteroleptic mer-[Cr(N∩N∩N)(CN)3] complexes: synthetic challenge, structural characterization and photophysical properties.

The substitution of three water molecules around trivalent chromium in CrBr3·6H2O with the tridentate 2,2':6',2''-terpyridine (tpy), N,N'-dimethyl-N,N'-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br3] complexes. Stepwise treatments with Ag(CF3SO3) and KCN under microwave irradiations provide mer-[Cr(L)(CN)3] in moderate yields. According to their X-ray crystal structures, the associated six-coordinate meridional [CrN3C3] chromophores increasingly deviate from a pseudo-octahedral arrangement according to L = ddpd ≈ dpq ≪ tpy; a trend in line with the replacement of six-membered with five-membered chelate rings around CrIII. Room-temperature ligand-centered UV-excitation at 18 170 cm-1 (λexc = 350 nm), followed by energy transfer and intersystem crossing eventually yield microsecond metal-centered Cr(2E → 4A2) phosphorescence in the red to near infrared domain 13 150-12 650 cm-1 (760 ≤ λem ≤ 790 nm). Decreasing the temperature to liquid nitrogen (77 K) extends the emission lifetimes to reach the millisecond regime with a record of 4.02 ms for mer-[Cr(dqp)(CN)3] in frozen acetonitrile.

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.

Bottom-Up Approach for the Rational Loading of Linear Oligomers and Polymers with Lanthanides.

The adducts between luminescent lanthanide tris(ß-diketonate)s and diimine or triimine ligands have been explored exhaustively for their exceptional photophysical properties. Their formation, stability, and structures in solution, together with the design of extended metallopolymers exploiting these building blocks, remain, however, elusive. The systematic peripheral substitution of tridentate 2,6-bis(benzimidazol-2-yl)pyridine binding units (Lk = L1-L5), taken as building blocks for linear oligomers and polymers, allows a fine-tuning of their affinity toward neutral [Ln(hfa)3] (hfa = hexafluoroacetylacetonate) lanthanide containers in the [LkLn(hfa)3] adducts. Two trends emerge with (i) an unusual pronounced thermodynamic selectivity for midrange lanthanides (Ln = Eu) and (ii) an intriguing influence of remote peripheral substitutions of the benzimidazole rings on the affinity of the tridentate unit for [Ln(hfa)3]. These trends are amplified upon the connection of several tridentate binding units via their benzimidazole rings to give linear segmental dimers (L6) and trimers (L7), which are considered as models for programming linear Wolf-Type II metallopollymers. Modulation of the affinity between the terminal and central binding units in the linear multitridentate ligands deciphers the global decrease of metal-ligand binding strengths with an increase in the length of the receptors (monomer → dimer → trimer → polymer). Application of the site binding model shed light onto the origin of the variation of the thermodynamic affinities: a prerequisite for the programmed loading of a polymer backbone with luminescent lanthanide ß-diketonates. Analysis of the crystal structures for these adducts reveals delicate correlations between the chemical bond lengths measured in the solid state (or bond valence parameters) and the metal-ligand affinities operating in solution.

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.

A Near-Infrared-II Emissive Chromium(III) Complex.

The combination of π-donating amido with π-accepting pyridine coordination units in a tridentate chelate ligand causes a strong nephelauxetic effect in a homoleptic CrIII complex, which shifts its luminescence to the NIR-II spectral range. Previously explored CrIII polypyridine complexes typically emit between 727 and 778 nm (in the red to NIR-I spectral region), and ligand design strategies have so far concentrated on optimizing the ligand field strength. The present work takes a fundamentally different approach and focusses on increasing metal-ligand bond covalence to shift the ruby-like 2 E emission of CrIII to 1067 nm at 77 K.

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.

Bright Long-Lived Circularly Polarized Luminescence in Chiral Chromium(III) Complexes.

A series of highly emissive inert and chiral CrIII complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized. The helical [Cr(dqpR)2 ]3+ (dqp=2,6-di(quinolin-8-yl)pyridine; R=OCH3 , Br or C≡CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC. The corresponding enantiomers show large glum ≈0.2 and high quantum yield of up to 17 %, which afford important CPL brightness of up to 170 m-1 cm-1 , a key point for applications as chiral luminescent probes. Moreover, the long-lived CP-NIR emission provided by these chromophores (ms range) in aqueous solution opens the way toward the quantification of chiral targets in biological systems with time-gated detection. Thus, such chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal-based complexes.