Chiroptical activity of benzannulated N-heterocyclic carbene rhenium(I) tricarbonyl halide complexes: towards efficient circularly polarized luminescence emitters.

The design of enantiomerically pure circularly polarized luminescent (CPL) emitters would enormously benefit from the accurate and in-depth interpretation of the chiroptical properties by means of jointly (chiroptical) photophysical measurements and state-of-the-art theoretical investigation. Herein, computed and experimental (chiro-)optical properties of a series of eight enantiopure phosphorescent rhenium(I) tricarbonyl complexes are systematically compared in terms of electronic circular dichroism (ECD) and CPL. The compounds have general formula fac-[ReX(CO)3(N^CNHC)], where N^CNHC is a pyridyl benzannulated N-heterocyclic carbene deriving from a (substituted) 2-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium proligand and X = Cl, Br and I, and display structured red phosphorescence with long-lived (τ = 7.0-19.1 µs) excited-state lifetime and dissymmetry factors |gLum| up to 4 × 10-3. The mixing of the character of the lowest-lying emitting triplet excited state is finely modulated between ligand centred (3LC), metal-to-ligand charge transfer (3MLCT) and halogen-to-ligand charge transfer (3XLCT) by the nature of the ancillary halogen and the chromophoric N^CNHC ligand. The study unravels the effect exerted by the nature of the excited state onto the ECD and CPL activity and will help to pave the way to construct efficient CPL emitters by chemical design.

Theoretical and DFT Study of Atypical Pentanuclear [(iPr3P)Ni]5Hn (n = 4, 6, 8) Clusters: What are the Rules?

The structure, bonding, and properties of a series of atypical pentanuclear nickel hydride clusters supported by electron-rich iPr3P of the type [(iPr3P)Ni]5Hn (n = 4, 6, 8; H4, H6, H8) and their anionic models where iPr3P are substituted by H- (H4', H6', H8') were investigated by density functional theory (DFT) calculations. All clusters were calculated to adopt a similar square pyramidal core geometry. Calculations indicate singlet ground states with small singlet-triplet gaps for H4 and H6, similar to previously reported experimental values. Molecular orbital theory description clusters were investigated using the simplified model complexes [HNi]5Hn5- (n = 4, 6, 8; H4', H6', H8'). The results show that there are three skeletal electron pairs (SEPs) in H4'. The addition of two molecules of H2 to form H6' and H8' results in the partial or full occupation of two degenerate MOs (e* set) that give two SEPs and one SEP, respectively. Indeed, the occupation of these low-lying weakly antibonding orbitals governs the multielectron chemistry available for these clusters and plays a role in their unique reactivity.

In-situ spectroscopic probe of the intrinsic structure feature of single-atom center in electrochemical CO/CO2 reduction to methanol.

While exploring the process of CO/CO2 electroreduction (COxRR) is of great significance to achieve carbon recycling, deciphering reaction mechanisms so as to further design catalytic systems able to overcome sluggish kinetics remains challenging. In this work, a model single-Co-atom catalyst with well-defined coordination structure is developed and employed as a platform to unravel the underlying reaction mechanism of COxRR. The as-prepared single-Co-atom catalyst exhibits a maximum methanol Faradaic efficiency as high as 65% at 30 mA/cm2 in a membrane electrode assembly electrolyzer, while on the contrary, the reduction pathway of CO2 to methanol is strongly decreased in CO2RR. In-situ X-ray absorption and Fourier-transform infrared spectroscopies point to a different adsorption configuration of *CO intermediate in CORR as compared to that in CO2RR, with a weaker stretching vibration of the C-O bond in the former case. Theoretical calculations further evidence the low energy barrier for the formation of a H-CoPc-CO- species, which is a critical factor in promoting the electrochemical reduction of CO to methanol.

Zwitterionic Mixed-Valence Species for the Design of Neutral Clocked Molecular Quantum-Dot Cellular Automata.

Mixed-valence compounds can be used for the design of molecular quantum-dot cellular automata (QCA). Here, we investigate the QCA properties of a three-dot "Y"-shaped functionalized zwitterionic neutral closo-carborane model 1-(3,5-{Cp(dHpe)Fe-C≡C-}2(C6H3))-10-Cp(dHpe)Fe-C≡C-closo-1-CB9H8 (1) (Cp = cyclopentadienyl (η5-C5H5) and dHpe = 1,2-bis(phosphino)ethane (H2PCH2CH2PH2)) as a neutral clocked molecular half-cell. DFT results clearly demonstrate that 1 can display simultaneously the two most basic properties necessary for clocked QCA operation, i.e., bistable switching behavior and clocked control. This is possible due to the three stable states (two active and one null) of 1, corresponding to occupation of each of the three iron-ethynyl groups by the positive charge. In addition, the proximal electronic bias effects can be overcome by the zwitterionic nature of 1, which could be imposed by external counterions, rendering these effects more predictable.

Synthesis, characterization and third-order nonlinear optical properties of a dodecaruthenium organometallic dendrimer with a zinc(ii) tetraphenylporphyrin core.

A new Zn(ii) porphyrin-based dendrimer (52) containing twelve Ru(ii) alkynyl fragments, has been prepared following a convergent approach in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) (6). The cubic nonlinear optical (NLO) properties of 52 and other derivatives of 6 have been measured by third-harmonic generation (THG) at 1907 nm and by Z-scan over the spectral range 500-1700 nm, revealing the remarkable NLO response of 52 in the near-IR range. These results highlight the beneficial role of the extended "cross fourchée"-like polymetallic structure of 52 on its third-order NLO properties.

Push-pull D-π-Ru-π-A chromophores: synthesis and electrochemical, photophysical and second-order nonlinear optical properties.

The present work describes the one-pot synthesis and electrochemical, photophysical and second-order nonlinear optical (NLO) properties of a series of dipolar π-delocalized Ru(ii) dialkynyl complexes. The eight new asymmetrical D-π-Ru-π-A push-pull chromophores incorporate pyranylidene ligands as pro-aromatic donor groups (D) and formaldehyde, indane-1,3-dione, pyrimidine or pyrimidinium as electron-attracting groups (A) separated by ruthenium bis-acetylide fragments and π-conjugated linkers. The second-order nonlinear optical (NLO) properties of all eight complexes were determined by the Electric-Field-Induced Second Harmonic generation (EFISH) technique (operating at 1907 nm), and were compared to those of their purely organic analogs. All investigated compounds (organic and organometallic) exhibited positive µß values, which dramatically increased for the complexes due to the presence of ruthenium in the π-conjugated core. The second-order NLO response could also be easily modulated by changing the nature of alkynyl substituents. The most promising ruthenium complexes 7 and 8 of the series with the pyrimidinium fragment displayed µß values of 14 000 × 10-48 esu. The effect of structural modifications on the redox and spectroscopic properties of the complexes was also studied. The intramolecular charge transfer (ICT) occurring through the ruthenium center of the push-pull σ-dialkynyl complexes was investigated by combining experimental and theoretical data.

Enhanced Cooperativity in Supported Spin-Crossover Metal-Organic Frameworks.

The impact of surface deposition on cooperativity is explored in Au(111)-supported self-assembled metal-organic frameworks (MOFs) based on Fe(II) ions. Using a thermodynamic model, we first demonstrate that dimensionality reduction combined with deposition on a metal surface is likely to deeply enhance the spin-crossover cooperativity, going from γ3D = 16 K for the bulk material to γ2Dsupp = 386 K for its 2D supported derivative. On the basis of density functional theory, we then elucidate the electronic structure of a promising Fe-based MOF. A chemical strategy is proposed to turn a weakly interacting magnetic system into a strongly cooperative spin-crossover monolayer with γMOFAu(111) = 83 K. These results open a promising route to the fabrication of cooperative materials based on SCO Fe(II) platforms.