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.

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.

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.

Anchoring of Metal Complexes on Au25 Nanocluster for Enhanced Photocoupled Electrocatalytic CO2 Reduction.

Atomically precise Au nanoclusters (NCs) with discrete energy levels can be used as photosensitizers for CO2 reduction. However, tight ligand capping of Au NCs hinders CO2 adsorption on its active sites. Here, a new hybrid material is obtained by anchoring of thiol functionalized terpyridine metal complexes (metal=Ru, Ni, Fe, Co) on Au NCs by ligand exchange reactions (LERs). The anchoring of Ru and Ni complexes on Au25 NC (Au25 -Ru and Au25 -Ni) leads to adequate CO2 to CO conversion for photocoupled electrocatalytic CO2 reduction (PECR) in terms of high selectivity, with Faradaic efficiency of CO (FECO ) exceeding 90 % in a wide potential range, remarkable activity (CO production rate up to two times higher than that for pristine Au25 PET18 ) and extremely large turnover frequencies (TOFs, 63012 h-1 at -0.97 V for Au25 -Ru and 69989 h-1 at -1.07 V vs. RHE for Au25 -Ni). Moreover, PECR stability test indicates the excellent long-term stability of the modified NCs in contrast with pristine Au NCs. The present approach offers a novel strategy to enhance PECR activity and selectivity, as well as to improve the stability of Au NCs under light illumination, which paves the way for highly active and stable Au NCs catalysts.

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.

Engineering ligand chemistry on Au25 nanoclusters: from unique ligand addition to precisely controllable ligand exchange.

Au25 nanoclusters (NCs) protected by 18 thiol-ligands (Au25SR18, SR is a thiolate ligand) are the prototype of atomically precise thiolate-protected gold NCs. Studies concerning the alteration of the number of surface ligands for a given Au25SR18 NC are scarce. Herein we report the conversion of hydrophobic Au25PET18 (PET = 2-phenylethylthiolate) NCs to Au25SR19 [Au25PET18(metal complex)1] induced by ligand exchange reactions (LERs) with thiolated terpyridine-metal complexes (metal complex, metal = Ru, Fe, Co, Ni) under mild conditions (room temperature and low amounts of incoming ligands). Interestingly, we found that the ligand addition reaction on Au25PET18 NCs is metal dependent. Ru and Co complexes preferentially lead to the formation of Au25SR19 whereas Fe and Ni complexes favor ligand exchange reactions. High-resolution electrospray ionization mass spectrometry (HRESI-MS) was used to determine the molecular formula of Au25SR19 NCs. The photophysical properties of Au25PET18(Ru complex)1 are distinctly different from Au25PET18. The absorption spectrum is drastically changed upon addition of the extra ligand and the photoluminescence quantum yield of Au25PET18(Ru complex)1 is 14 times and 3 times higher than that of pristine Au25PET18 and Au25PET17(Ru complex)1, respectively. Interestingly, only one surface ligand (PET) could be substituted by the metal complex when neutral Au25PET18 was used for ligand exchange whereas two ligands could be exchanged when starting with negatively charged Au25PET18. This charge dependence provides a strategy to precisely control the number of exchanged ligands at the surface of NCs.

Multistate Aggregation-Induced Chiroptical Properties of Enantiopure Disulfide-Mediated Bispyrene Macrocycles.

A chiral bispyrene macrocycle designed for exclusive intermolecular excimer fluorescence upon aggregation was synthesized by a double hydrothiolation of a bis-enol ether macrocycle followed by intramolecular oxidation of free thiols. Unusually high stereoselectivity was achieved for the thiol-ene additions under templated conditions and Et3 B/O2 radical initiation. After enantiomer separation (chiral stationary phase HPLC), aqueous conditions provoked aggregation. Detailed structural evolution was afforded by ECD/CPL monitoring. Three regimes can be observed and characterized by strong modifications in chiroptical patterns under, at, or above a 70 % H2 O : THF threshold. In luminescence, high glum dissymmetry factors values were obtained, up to 0.022, as well as a double sign inversion of CPL signals during the aggregation, a behavior rationalized by time-dependent density functional theory (TDDFT) calculations. Langmuir layers of enantiopure disulfide macrocycles were formed at the air-water interface and transferred onto solid substrates to afford Langmuir-Blodgett films, which were then studied by AFM and UV/ECD/fluorescence/CPL.

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.

Advanced Catalyst for CO2 Photo-Reduction: From Controllable Product Selectivity by Architecture Engineering to Improving Charge Transfer Using Stabilized Au Clusters.

Despite enormous progress and improvement in photocatalytic CO2 reduction reaction (CO2 RR), the development of photocatalysts that suppress H2 evolution reaction (HER), during CO2 RR, remains still a challenge. Here, new insight is presented for controllable CO2 RR selectivity by tuning the architecture of the photocatalyst. Au/carbon nitride with planar structure (p Au/CN) showed high activity for HER with 87% selectivity. In contrast, the same composition with a yolk@shell structure (Y@S Au@CN) exhibited high selectivity of carbon products by suppressing the HER to 26% under visible light irradiation. Further improvement for CO2 RR activity was achieved by a surface decoration of the yolk@shell structure with Au25 (PET)18 clusters as favorable electron acceptors, resulting in longer charge separation in Au@CN/Auc Y@S structure. Finally, by covering the structure with graphene layers, the designed catalyst maintained high photostability during light illumination and showed high photocatalytic efficiency. The optimized Au@CN/Auc /G Y@S structure displays high photocatalytic CO2 RR selectivity of 88%, where the CO and CH4 generations during 8 h are 494 and 198 µmol/gcat., respectively. This approach combining architecture engineering and composition modification provides a new strategy with improved activity and controllable selectivity toward targeting applications in energy conversion catalysis.

Exceptionally Stable Dimers and Trimers of Au25 Clusters Linked with a Bidentate Dithiol: Synthesis, Structure and Chirality Study.

A bidentate chiral dithiol (diBINAS) is utilised to bridge Au25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by small-angle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed self-assembly of metal clusters.

Insight into the transient inactivation effect on Au/TiO2 catalyst by in-situ DRIFT and UV-vis spectroscopy.

Au catalysts have drawn broad attention for catalytic CO oxidation. However, a molecular-level understanding of the reaction mechanism on a fast time-resolved scale is still lacking. Herein, we apply in situ DRIFTS and UV-Vis spectroscopy to monitor the rapid dynamic changes during CO oxidation over Au/TiO2. A pronounced transient inactivation effect likely due to a structural change of Au/TiO2 induced by the reactants (CO and O2) is observed at the beginning of the reaction. The transient inactivation effect is affected by the ratio of CO and O2 concentrations. More importantly, during the unstable state, the electronic properties of the Au particles change, as indicated by the shift of the CO stretching vibration. UV-Vis spectroscopy corroborates the structure change of Au/TiO2 surface induced by the reactants, which leads to a weakening of the Au catalyst's ability to be oxidized (less O2 adsorption), resulting in the transient inactivation effect.

Beyond the Threshold: A Study of Chalcogenophene-Based Two-Photon Initiators.

A series of nine soluble, symmetric chalcogenophenes bearing hexyl-substituted triphenylamines, indolocarbazoles, or phenylcarbazoles was designed and synthesized as potential two-photon absorption (2PA) initiators. A detailed photophysical analysis of these molecules revealed good 2PA properties of the series and, in particular, a strong influence of selenium on the 2PA cross sections, rendering these materials especially promising new 2PA photoinitiators. Structuring and threshold tests proved the efficiency and broad spectral versatility of two selenium-containing lead compounds as well as their applicability in an acrylate resin formulation. A comparison with commercial photoinitiators Irg369 and BAPO as well as sensitizer ITX showed that the newly designed selenium-based materials TPA-S and TPA-BBS outperform these traditional initiators by far both in terms of reactivity and dose. Moreover, by increasing the ultralow concentration of TPA-BBS, a further reduction of the polymerization threshold can be achieved, revealing the great potential of this series for application in two-photon polymerization (2PP) systems where only low laser power is available.

Bimolecular photo-induced electron transfer enlightened by diffusion.

Photochemical electron transfer between freely diffusing molecules has been studied extensively. Here, we try to elucidate how much these works have contributed to the understanding of electron transfer. To this end, we have revisited the work performed in the experimental and theoretical areas of concern from the beginning of the 20th century up to the present day. We present a critical look at the major contributions and compile the current picture of a variety of phenomena around electron transfer in solution. This is based on two main developments, besides the theory of Marcus: encounter theories of diffusion and laser techniques in time-resolved spectroscopy.

Bimolecular photoinduced electron transfer in non-polar solvents beyond the diffusion limit.

Electron transfer (ET) quenching dynamics in non-polar solvents are investigated using ultrafast spectroscopy with a series of six fluorophore/quencher pairs, covering a driving force range of more than 1.3 eV. The intrinsic ET rate constants, k0, deduced from the quenching dynamics in the static regime, are of the order of 1012-1013 M-1 s-1, i.e., at least as large as in acetonitrile, and do not exhibit any marked dependence on the driving force. A combination of transient electronic and vibrational absorption spectroscopy measurements reveals that the primary product of static quenching is a strongly coupled exciplex that decays within a few picoseconds. More weakly coupled exciplexes with a longer lifetime are generated subsequently, during the dynamic, diffusion-controlled, stage of the quenching. The results suggest that static ET quenching in non-polar solvents should be viewed as an internal conversion from a locally excited state to a charge-transfer state of a supermolecule rather than as a non-adiabatic ET process.

Solvent tuning of photochemistry upon excited-state symmetry breaking.

The nature of the electronic excited state of many symmetric multibranched donor-acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A-(π-D)2,3 molecules with photoisomerizable A-π-D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2 ← S1 electronic transition, whose energy reflects interbranch coupling. It occurs in all but nonpolar solvents. In polar media, it is rapidly followed by an alkyne-allene isomerization of the excited branch. In nonpolar solvents, slow and reversible isomerization corresponding to chemically-driven symmetry breaking, is observed. These findings reveal that the photoreactivity of large conjugated molecules can be tuned by controlling the localization of the excitation.

Broadband fluorescence reveals mechanistic differences in excited-state proton transfer to protic and aprotic solvents.

Excited-state proton transfer (ESPT) to solvent is often explained according to the two-step Eigen-Weller model including a contact ion pair (CIP*) as an intermediate, but general applicability of the model has not been thoroughly examined. Furthermore, examples of the spectral identification of CIP* are scarce. Here, we report on a detailed investigation of ESPT to protic (H2O, D2O, MeOH and EtOH) and aprotic (DMSO) solvents utilizing a broadband fluorescence technique with sub-200 fs time resolution. The time-resolved spectra are decomposed into contributions from the protonated and deprotonated species and a clear signature of CIP* is identified in DMSO and MeOH. Interestingly, the CIP* intermediate is not observable in aqueous environment although the dynamics in all solvents are multi-exponential. Global analysis based on the Eigen-Weller model is satisfactory in all solvents, but the marked mechanistic differences between aqueous and organic solvents cast doubt on the physical validity of the rate constants obtained.

Propyl acetate/butyronitrile mixture is ideally suited for investigating the effect of dielectric stabilization on (photo)chemical reactions.

Characterization of propyl acetate/butyronitrile (PA/BuCN) mixtures by various spectroscopic techniques is described. The neat solvents have identical viscosities and refractive indices but their dielectric constants differ significantly. Detailed solvatochromic and titration data show that the mixtures do not exhibit specific solute-solvent interactions or significant dielectric enrichment effects. Therefore, the mixtures are ideally suited for investigating the effect of dielectric stabilization on (photo)chemical reactions. Dynamic Stokes shift experiments performed on two push-pull probes demonstrate that the solvation dynamics are significantly decelerated in the mixtures as compared to the neat solvents. Therefore, the mixtures allow for varying both the extent and time scale of the dielectric stabilization in a predictable manner.

Halogen-Bond Assisted Photoinduced Electron Transfer.

The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor-donor-acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927-3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski-Collins-Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.