Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes

LA/P/0056/2020. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). FCT is acknowledged for PTDCQUI-QIN0252_2021 (PNM). The CARISMA COST action CM1205 is acknowledged. MJC thanks N. A. G. Bandeira for technical assistance. The CATSUS doctoral programme is also acknowledged. Publisher Copyright: © 2023 The Royal Society of Chemistry.Cyclic voltammetry and bulk electrolysis showed that [Ni(ii)(salphen)] [1], [Ni(ii)(tBu-salphen)] [2], and a binuclear Ni(ii) compound combining salphen and tBu-salphen [3] react with CO2 to yield a metal-carbonyl species that is stable under an oxygen free atmosphere. Upon exposure to air, a stoichiometric amount of CO is released (detected by gas chromatography) and protonation regenerates the initial complex. To shed light on the mechanism of CO2 reduction and O2-dependent CO release by [1], UV-vis, EPR and SEC-IR spectroscopy studies complemented with DFT calculations were performed. It is proposed that the mono reduced [Ni(i)(salphen)]−, 2[1]−, formed a CO2 complex, 2[1(CO2)]−, which was then further reduced to 3[1(CO2)]2−. After addition of two protons, the coordinated CO2 was reduced to CO and released, regenerating 1[1]. Alternatively, 2[1(CO2)]− is protonated and then reduced to the same intermediate as before, continuing the same way. In the second cycle, the CO released competed with CO2 and coordinated to 2[1]− much more strongly, thereby deactivating the system. The new 2[1(CO)]− was reduced to 3[1(CO)]2− which was identified by comparison of experimental spectroscopic (UV-vis, EPR, SEC-IR) data with DFT calculated parameters.publishersversionpublishe

Accurate description of low-lying excited states in a series of photoreactive clusters [Os3(CO)10(α-diimine)] by DFT calculations

Density functional theory (DFT) calculations were performed on the clusters [Os3(CO)10(α-diimine)], for α-diimine = 2,2'-bipyridine (BPY), N-isopropyl 2-iminomethylpyridine (IMP), and N,N'-diisopropyl-l,4-diaza-1,3-butadiene (DAB), together with their spectroscopic study. This important family of clusters is known to convert upon irradiation with visible light into short-lived biradicals and long-lived zwitterions from a σ* (SBLCT) excited state that, however, has not been described accurately thus far by quantum mechanical calculations. Based on the combined DFT, UV-vis absorption and resonance Raman data, the lowest-lying visible absorption band is assigned to a σ(Os1–Os3)-to-*(α-diimine) CT transition for α-diimine = bpy and IMP, and to a strongly delocalized σ(Os1‒Os3)*-to-σ*(Os1‒Os3)* ¬transition for conjugated non-aromatic α-diimine = DAB. The DFT calculations rationalize the experimentally determined characteristics of this electronic transition in the studied series: (i) the corresponding absorption band is the dominant feature in the visible spectral region, (ii) the CT character of the electronic excitation declines from α-diimine = bpy to IMP and vanishes for DAB, (iii) the excitation energies decrease in the order α-diimine = DAB > BPY > IMP, (iv) the oscillator strength shrinks in the order α-diimine = DAB > IMP > BPY. Reference photoreaction quantum yields measured accurately for the formation of a cluster zwitterion from [Os3(CO)10(IMP)] in strongly coordinating pyridine, demonstrate that the optical population of the lowest-energy 1σ* and relaxed 3σ* excited states in the DFT model scheme is still capable of inducing the initial homolytic Os1‒Os3 σ-bond splitting, although less efficiently than the optical excitation into neighbor higher-lying electronic transitions due to a higher potential barrier for the reaction from a dissociative (σσ*) state

Group 6 complexes as electrocatalysts of CO2 reduction: strong substituent control of the reduction path of [Mo(η3-allyl)(CO)2(x,x′- dimethyl-2,2′-bipyridine)(NCS)] (x = 4-6)

A series of complexes [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)(NCS)] (dmbipy = dimethyl-2,2ʹ-bipyridine; x = 4-6) have been synthesized and their electrochemical reduction investigated using combined cyclic voltammetry (CV) and variable-temperature spectroelectrochemistry (IR/UV-vis SEC) in tetrahydrofuran (THF) and butyronitrile (PrCN), at gold and platinum electrodes. The experimental results, strongly supported by DFT calculations, indicate that the general cathodic path of these Group-6 organometallic complexes is closely related to that of the intensively studied class of Mn tricarbonyl α-diimine complexes, themselves recently identified as important smart materials for catalytic CO2 reduction. The dimethyl substitution on the 2,2ʹ-bipyridine ligand backbone has presented new insights into this emerging class of catalysts. For the first time, the 2e‒ reduced 5-coordinate anions [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)]‒ were directly observed with IR SEC. The role of steric and electronic effects in determining the reduction-induced reactivity was also investigated. For the 6,6′-dmbipy, the primary 1e‒ reduced radical anions exert unusual stability radically changing the follow up cathodic path. The 5-coordinate anion [Mo(η3-allyl)(CO)2)(6,6′-dmbipy)]‒ remains stable at low temperature in strongly coordinating butyronitrile and does not undergo dimerization at elevated temperature, in sharp contrast to reactive [Mo(η3-allyl)(CO)2)(4,4′-dmbipy)]‒ that tends to dimerize in a reaction with the parent complex. The complex with the 5,5′-dmbipy ligand combines both types of reactivity. Under aprotic conditions, the different properties of [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)]‒ are also reflected in their reactivity towards CO2. Preliminary CV and IR SEC results reveal differences in the strength of CO2 coordination at the free axial position. Catalytic waves attributed to the generation of the 5-coordinate anions were observed by CV, but only a modest catalytic performance towards the production of formate was demonstrated by IR SEC. For 6,6′-dmbipy, a stronger catalytic effect was observed for the Au cathode compared to Pt

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of 8-quinolinolato ligands with heavy-atoms substituents: synthesis, fluorescence and application in OLED devices

This work describes the synthesis and characterisation of new tetrahedral boron complexes, incorporating bromine- or iodine-substituted 8-quinolinolato chelate chromophores connected to 9-borafluoren-9-yl or diphenylboron orthogonal fragments. The molecular features and photophysical properties of these complexes are analysed in both solution and solid state. Steady-state photophysical studies reveal photoluminescence quantum yields (Φf) ranging from 0.02 to 0.15 and prompt fluorescence (PF) lifetimes (τf) between 2 and 16 ns. Time-resolved photophysical experiments show the presence of delayed fluorescence (DF) and phosphorescence at both 77 K and room temperature. The DF intensity increases with a rise in temperature. This variation is ascribed to an enhancement in the intersystem crossing (ISC) process promoted by the bromine or iodine heavy-atom effect. Investigations into the dependence of DF intensity relative to the excitation dose indicate emissions stemming either from Triplet-Triplet Annihilation (TTA), Thermally Activated Delayed Fluorescence (TADF), or a combination of these competing mechanisms. The effect is related to the size and number of heavy-atom substituents in each boron complex. A study of the DF emission intensity as a function of the excitation dose reveals that diiodo-substituted 8-quinolinolato boron complexes, whether rigid or flexible, display TADF emission. Rigid 5,7-dibromo- and 5-chloro-7-iodo-substituted 8-quinolinolato complexes exhibit a combined TADF-TTA mechanism, whereas the other complexes predominantly demonstrate pure TTA emission. DFT and TDDFT calculations showed that the ground state structures reproduced the experimental geometries and only small increases in bond lengths were observed in the excited state geometries. The low energy absorption bands displayed mainly intra-ligand π→π* (8-quinolinato) character. The fluorescence emission energies were well reproduced, while the singlet-triplet energy gaps were relatively high. Ultimately, organic light-emitting diodes (OLEDs) are fabricated using the most luminescent boron complexes. The best OLED is obtained when using complex 3a, which displays green electroluminescence (EL) (λEL = 502 nm) with maximum external quantum efficiency (EQEmax) of 2.5% and maximum luminance (Lmax) of 2200 cd m-2

cis-Dichloridobis­(5,5′-dimethyl-2,2′-bipyridine)­manganese(II) 2.5-hydrate

The metal site in the title compound [MnCl2(C12H12N2)2]·2.5H2O has a distorted octa­hedral geometry, coordinated by four N atoms of two 5,5′-dimethyl-2,2′-dipyridine ligands and two Cl atoms. Two and a half water molecules of hydration per complex unit are observed in the crystal structure. The compounds extend along the c axis with O—H⋯Cl, O—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds and π–π inter­actions [centroid-centroid distance = 3.70 (2) Å] contributing substanti­ally to the crystal packing. The Mn and one of the water O atoms, the latter being half-occupied, are located on special positions, in this case a rotation axis of order 2

One step forward towards the development of eco-friendly antifouling coatings: Immobilization of a sulfated marine-inspired compound

Marine biofouling represents a global economic and ecological challenge and few eco-friendly antifouling agents are available. The aim of this work was to establish the proof of concept that a recently synthesized nature-inspired compound (gallic acid persulfate, GAP) can act as an eco-friendly and effective antifoulant when immobilized in coatings through a non-release strategy, promoting a long-lasting antifouling effect. The synthesis of GAP was optimized to provide quantitative yields. GAP water solubility was assessed, showing values higher than 1000 mg/mL. GAP was found to be stable in sterilized natural seawater with a half-life (DT50) of 7 months. GAP was immobilized into several commercial coatings, exhibiting high compatibility with different polymeric matrices. Leaching assays of polydimethylsiloxane and polyurethane-based marine coatings containing GAP confirmed that the chemical immobilization of GAP was successful, since releases up to fivefold lower than the conventional releasing systems of polyurethane-based marine coatings were observed. Furthermore, coatings containing immobilized GAP exhibited the most auspicious anti-settlement effect against Mytilus galloprovincialis larvae for the maximum exposure period (40 h) in laboratory trials. Overall, GAP promises to be an agent capable of improving the antifouling activity of several commercial marine coatings with desirable environmental properties.This research was funded by national funds through the Foundation for Science and Technology (FCT) within the scope of research unit grants to CIIMAR (UIDB/04423/2020 and UIDP/04423/2020), to BioISI (UIDB/04046/2020 and UIDP/04046/2020) and under the project PTDC/AAG-TEC/0739/2014 (reference POCI-01-0145-FEDER-016793) supported through national funds provided by FCT and the European Regional Development Fund (ERDF) via the Programa Operacional Factores de Competitividade (POFC/COMPETE) programme and the Reforçar a Investigação, o Desenvolvimento Tecnológico e a Inovação (RIDTI; project 9471)

Effect of the 2-R-Allyl and Chloride Ligands on the Cathodic Paths of [Mo(η3-2-R-allyl)(α-diimine)(CO)2Cl] (R = H, CH3; α-diimine = 6,6′-Dimethyl-2,2′-bipyridine, Bis(p-tolylimino)acenaphthene)

The new, formally Mo(II) complexes [Mo(η3-2-R-allyl)(6,6′-dmbipy)(CO)2Cl] (6,6′-dmbipy = 6,6′-dimethyl-2,2′-bipyridine; 2-R-allyl = allyl for R = H, 2-methallyl for R = CH3) and [Mo(η3-2-methallyl)(pTol-bian)(CO)2Cl] (pTol-bian = bis(p-tolylimino)acenaphthene) share, in this rare case, the same structural type. The effect of the anionic π-donor ligand X (Cl– vs NCS–) and the 2-R-allyl substituents on the cathodic behavior was explored. Both ligands play a significant role at all stages of the reduction path. While 2e–-reduced [Mo(η3-allyl)(6,6′-dmbipy)(CO)2]− is inert when it is ECE-generated from [Mo(η3-allyl)(6,6′-dmbipy)(CO)2(NCS)], the Cl– ligand promotes Mo–Mo dimerization by facilitating the nucleophilic attack of [Mo(η3-allyl)(6,6′-dmbipy)(CO)2]− at the parent complex at ambient temperature. The replacement of the allyl ligand by 2-methallyl has a similar effect. The Cl–/2-methallyl ligand assembly destabilizes even primary radical anions of the complex containing the strongly π-accepting pTol-Bian ligand. Under argon, the cathodic paths of [Mo(η3-2-R-allyl)(6,6′-dmbipy)(CO)2Cl] terminate at ambient temperature with 5-coordinate [Mo(6,6′-dmbipy)(CO)3]2– instead of [Mo(η3-2-R-allyl)(6,6′-dmbipy)(CO)2]−, which is stabilized in chilled electrolyte. [Mo(η3-allyl)(6,6′-dmbipy)(CO)2]− catalyzes CO2 reduction only when it is generated at the second cathodic wave of the parent complex, while [Mo(η3-2-methallyl)(6,6′-dmbipy)(CO)2]− is already moderately active at the first cathodic wave. This behavior is fully consistent with absent dimerization under argon on the cyclic voltammetric time scale. The electrocatalytic generation of CO and formate is hampered by the irreversible formation of anionic tricarbonyl complexes replacing reactive [Mo(η3-2-methallyl)(6,6′-dmbipy)(CO)2]2 along the cathodic route

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of F- and Cl-substituted 8-quinolinolato ligands: synthesis, molecular and electronic structures, fluorescence and application in OLED devices

Six new four-coordinate tetrahedral boron complexes, containing 9-borafluoren-9-yl and diphenylboron cores attached to orthogonal fluorine- and chlorine-substituted 8-quinolinolato ligand chromophores, have been synthesised, characterised, and applied as emitters in organic light-emitting diodes (OLEDs). An extensive steady-state and time-resolved photophysical study, in solution and in the solid state, resulted in the first-time report of delayed fluorescence (DF) in solid films of 8-quinolinolato boron complexes. The DF intensity dependence on excitation dose suggests that this emission originates from triplet–triplet annihilation (TTA). Density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies give insight into the ground and excited state geometries, electronic structures, absorption energies, and singlet–triplet gaps in these new organoboron luminophores. Finally, given their highly luminescent behaviour, organic light-emitting diode (OLED) devices were produced using the synthesised organoboron compounds as emissive fluorescent dopants. The best OLED displays green-blue (λmaxEL = 489 nm) electroluminescence with an external quantum efficiency (EQE) of 3.3% and a maximum luminance of 6300 cd m−2

The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4

Funding Research was funded by Fundação para a Ciência e a Tecnologia (FCT): projects UIDB/00100/2020, UIDP/00100/2020, LA/P/0056/2020, UIDB/04046/2020, UIDP/04046/2020, UIDB/50006/2020, UIDP/50006/2020 and LA/P/0008/2020, UIDB/04378/2020, UIDP/04378/2020, and LA/P/0140/2020, PTDC/QUI-QFI/29236/2017, PTDCQUI-QIN0252_2021, CEECIND/00509/2017; Fonds de la Recherche Scientifique (FNRS): PDR T.0095.21); Portugal2020: CENTRO-01-0145-FEDER-000018; Royal Society of Chemistry (RSC): R21-7511142525. Acknowledgments Centro de Química Estrutural (CQE) and Institute of Molecular Sciences (IMS) acknowledge the financial support of Fundação para a Ciência e a Tecnologia (FCT): Projects UIDB/00100/2020, UIDP/00100/2020, and LA/P/0056/2020, respectively. BioISI acknowledges FCT for financial support (UIDB/04046/2020, UIDP/04046/2020). This work was supported by the FNRS (PDR T.0095.21). Clara S. B. Gomes acknowledges the Associate Laboratory for Green Chemistry—LAQV, the Applied Molecular Biosciences Unit—UCIBIO and Associated Laboratory i4HB, which are financed by national funds from FCT (UIDB/50006/2020, UIDP/50006/2020 and LA/P/0008/2020, UIDB/04378/2020 and UIDP/04378/2020, and LA/P/0140/2020, respectively). Sónia Barroso thanks project SmartBioR for financial support (CENTRO-01-0145-FEDER-000018)and Centro de Química Estrutural for the access to crystallography facilities. Nuno A. G. Bandeira gratefully acknowledges the NanoBioSolutions FCT grant PTDC/QUI-QFI/29236/2017 for the computational infrastructure. Paulo N. Martinho thanks FCT and RSC for financial support (grants PTDCQUI-QIN0252_2021 and R21-7511142525). Paulo N. Martinho also thanks FCT for the contract CEECIND/00509/2017.Complexes [Fe(X-salEen)2]BPh4·DMF, with X = Br (1), Cl (2), and F (3), were crystallised from N,N′-dimethylformamide with the aim of understanding the role of a high boiling point N,N′-dimethylformamide solvate in the spin crossover phenomenon. The counter ion was chosen for only being able to participate in weak intermolecular interactions. The compounds were structurally characterised by single crystal X-ray diffraction. Complex 1 crystallised in the orthorhombic space group P212121, and complexes 2 and 3 in the monoclinic space group P21/n. Even at room temperature, low spin was the predominant form, although complex 2 exhibited the largest proportion of the high-spin species according to both the magnetisation measurements and the Mössbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes 1–3 and the iodide analogue 4. While all approaches reproduced the experimental structures very well, the energy balance between the high-spin and low-spin forms was harder to reproduce, though some calculations pointed to the easier spin crossover of complex 2, as observed. Periodic calculations with the functional PBE led to very similar ΔEHS-LS values for all complexes but showed a preference for the low-spin form. However, the single-point calculations with B3LYP* showed, for the model without solvate, that the Cl complex should undergo spin crossover more easily. The molecular calculations also reflected this fact, which was more clearly defined when the cation–anion–solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes.publishersversionpublishe

Electron-Transfer-Induced Side-Chain Cleavage in Tryptophan Facilitated through Potassium-Induced Transition-State Stabilization in the Gas Phase

Fragmentation of transient negative ions of tryptophan molecules formed through electron transfer in collisions with potassium atoms is presented for the first time in the laboratory collision energy range of 20 up to 100 eV. In the unimolecular decomposition process, the dominating side-chain fragmentation channel is assigned to the dehydrogenated indoline anion, in contrast to dissociative electron attachment of free low-energy electrons to tryptophan. The role of the collision complex formed by the potassium cation and tryptophan negative ion in the electron transfer process is significant for the mechanisms that operate at lower collision energies. At those collision times, on the order of a few tens of fs, the collision complex may not only influence the lifetime of the anion but also stabilize specific transition states and thus alter the fragmentation patterns considerably. DFT calculations, at the BHandHLYP/6-311++G(3df,2pd) level of theory, are used to explore potential reaction pathways and the evolvement of the charge distribution along those.F.F.d.S., T.C., and A.R. acknowledge the Portuguese National Funding Agency FCT-MCTES for IF-FCT IF/00380/2014, SFRH/BD/52538/2014, and PD/BD/114449/2016 and together with P.L.-V. the research grants PTDC/FIS-AQM/31215/2017 and PTDC/FIS-AQM/31281/2017. This work was also supported by Radiation Biology and Biophysics Doctoral Training Programme (RaBBiT, PD/00193/2012); UIDB/00068/2020 (CEFITEC) and UIDB/04378/2020 (UCIBIO). M.J.C. and A.G. also thank FCT-MCTES UIDB/04046/2020 and UIDP/04046/2020, and A.G. thanks the SFRH/BPD/89722/2012 grant. G.G. is partially funded by the Spanish Ministerio de Ciencia, Innovacion y Universidades (project no. PID2019-104727RB-C21) and CSIC (Project LINKA20085). O.I. acknowledges the Icelandic Center of Research (RANNIS) and the University of Iceland Research Fund for financial support. The authors thank Ragnar Bjornsson for fruitful discussions while preparing this manuscript.Pre-prin