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Hofmann-like cyanometallic complexes represent one of the biggest and well-known classes of FeII spin-crossover compounds. In this paper, we report on the first FeII Hofmann clathrate analogues with unsubstituted 1,2,3-triazole, which exhibit temperature induced spin transition. Two new coordination polymers with the general formula [FeII(1,2,3-triazole)2MII(CN)4] (M = Pt, Pd) undergo abrupt hysteretic spin crossover in the range of 190-225 K as revealed by magnetic susceptibility measurements. Two compounds are isostructural and are built of infinite cyanometallic layers which are supported by 1,2,3-triazole ligands. The thermal hysteresis loop is very stable at different scan rates from 0.5 to 10 K min-1. The compounds display strong thermochromic effect, changing their colour from pink in the low-spin state to white in the high-spin state. Our findings show that 1,2,3-triazole is suitable for elaboration of spin-crossover Hofmann clathrate analogues, and its use instead of more classical azines can advantageously expand this family of complexes.Developing highly active electrocatalysts with low costs and long durability for oxygen evolution reactions (OERs) is crucial towards the practical implementations of electrocatalytic water-splitting and rechargeable metal-air batteries. Anodized nanostructured 3d transition metals and alloys with the formation of OER-active oxides/hydroxides are known to have high catalytic activity towards OERs but suffer from poor electrical conductivity and electrochemical stability in harsh oxidation environments. Here we report that high OER activity can be achieved from the metallic state of Ni which is passivated by atomically thick graphene in a three-dimensional nanoporous architecture. As a free-standing catalytic anode, the non-oxide transition metal catalyst shows a low OER overpotential, high OER current density and long cycling lifetime in alkaline solutions, benefiting from the high electrical conductivity and low impedance resistance for charge transfer and transport. This study may pave a new way to develop high efficiency transition metal OER catalysts for a wide range of applications in renewable energy.Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene using a Cu(ii) 7-amino-6-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile to create cyclohexenone and H2O as products. After the initial H-atom abstraction step, two different reaction pathways have been identified that are distinguished by the participation of alkyl hydroperoxide (referred to as the "open" cycle) versus the methanol side-product (referred to as the "closed" cycle) within the catalyst recovery process. Importantly, both pathways involve dehydrogenation and re-hydrogenation of the -NH2 group bound to the Cu-site - a feature that is revealed from the ensemble sampling of configurations of the reactive species that are stabilized within the explicit solvent environment of the simulation. Estimation of the energy span from the experimental turnover frequency yields an approximate value of 22.7 kcal mol-1 at 350 K. Whereas the closed cycle value is predicted to be 26.2 kcal mol-1, the open cycle value at 16.5 kcal mol-1. Both pathways are further consistent with the equilibrium between Cu(ii) and Cu(iii) that has previously been observed. In comparison to prior static DFT calculations, the ensemble of both solute and solvent configurations has helped to reveal a breadth of processes that underpin the full catalytic cycle yielding a more comprehensive understanding of the importance of radical reactions and catalysis recovery.Herein, we report on the synthesis, structural analysis, physicochemical characterization and photoluminescence performance of two ternary compounds based on dicarboxylate and bispyridyl-like ligands and metal ions of group 12, namely [Zn2(μ4-bdc)(μ-pbptz)(DMF)2(NO3)2]n (1-Zn) and [Cd(μ3-bdc)(μ-pbptz)]·DMFn (2-Cd) (where bdc = benzene-1,4-dicarboxylate, pbptz = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and DMF = N,N-dimethylformamide). Bay K 8644 manufacturer 1-Zn, consisting of a 2D-layered framework, can be considered as the lower-dimensional analogue of the previously reported [Zn2(μ4-bdc)2(μ-pbptz)]·2DMF·3H2On 3D MOF (1'-Zn), which is shown to recrystallize into 1-Zn undergoing a kind of exfoliation. 2-Cd presents a 3D doubly interpenetrated framework whose porosity is reduced to approximately half of the available solvent-accessible voids contained in the non-interpenetrated homologue reported so far, [Cd(μ3-bdc)(μ-pbptz)]·3DMFn (2'-Cd). Structural factors leading to each of the alternative frameworks are detailed by analysing the building units with a perusal of the Cambridge Structural Database and providing a comparative description of the structures. The photoluminescence properties of herein reported compounds (1-Zn and 2-Cd) are also measured and the processes governing the spectra are described using time-dependent density-functional theory (TD-DFT), which allows establishing some structural correspondences by comparing these results with those of the 1'-Zn and 2'-Cd analogues.Reaction of the complexes [Fe2(μ2-NP(pip)3)2(NP(pip)3)2] (1-Fe) and [Co2(μ2-NP(pip)3)2(NP(pip)3)2] (1-Co), where [NP(pip)3]1- is tris(piperidinyl)imidophosphorane, with nitrous oxide, S8, or Se0 results in divergent reactivity. With nitrous oxide, 1-Fe forms [Fe2(μ2-O)(μ2-NP(pip)3)2(NP(pip)3)2] (2-Fe), with a very short Fe3+-Fe3+ distance. Reactions of 1-Fe with S8 or Se0 result in the bridging, side-on coordination (μ-κ1κ1-E22-) of the heavy chalcogens in complexes [Fe2(μ-κ1κ1-E2)(μ2-NP(pip)3)2(NP(pip)3)2] (E = S, 3-Fe, or Se, 4-Fe). In all cases, the complex 1-Co is inert.Sequence-selective recognition of cationic amphipathic peptides by synthetic receptors is significant to biological applications, but it is still a great challenging task. Here we first study the binding characteristics of receptor cucurbit[7]uril (CB[7]) to the smallest aromatic tripeptides X1GG (X1 = tryptophan (W), phenylalanine (F), and tyrosine (Y)) and basic tripeptides X2GG (X2 = arginine (R), lysine (K), and histidine (H)) by molecular dynamics simulations. The study indicates that the sidechains of aromatic X1 residues can be encapsulated into the CB[7] cavity, while the sidechains of basic X2 residues prefer to locate at the CB[7] portal. Based on that, we consider hydrophobic aromatic residues as the N-terminus, the smallest glycine (G) as the 2nd-residue and basic residues as the C-terminus, and design nine tripeptides X1GX2 (X1 = F, Y, W and X2 = H, K, R). We found that there is a great influence of the C-terminal basic residue of X1GX2 on binding with CB[7] due to the introduction of a new binding site between CB[7] and the sidechain of the C-terminal residue. Interestingly, CB[7] can differentiate WGR and WGK with similar structures efficiently because of their eight orders of magnitude difference in the association constant (Ka). Besides, for WGR, YGR, and YGK with a nanomolar binding affinity (Ka > 109 M-1), on reversing the sequence order of the 2nd-residue and 3rd-residue, their Ka reduces by about at least 1000-fold, implying the sequence dependence of CB[7] on recognizing these tripeptides. These results predict the potential applications of CB[7] in recognizing cationic amphipathic peptides.Microporous zeolite-type materials, with crystalline porous structures formed by well-defined channels and cages of molecular dimensions, have been widely employed as heterogeneous catalysts since the early 1960s, due to their wide variety of framework topologies, compositional flexibility and hydrothermal stability. The possible selection of the microporous structure and of the elements located in framework and extraframework positions enables the design of highly selective catalysts with well-defined active sites of acidic, basic or redox character, opening the path to their application in a wide range of catalytic processes. This versatility and high catalytic efficiency is the key factor enabling their use in the activation and conversion of different alkanes, ranging from methane to long chain n-paraffins. Alkanes are highly stable molecules, but their abundance and low cost have been two main driving forces for the development of processes directed to their upgrading over the last 50 years. However, the availability of advanced characterization tools combined with molecular modelling has enabled a more fundamental approach to the activation and conversion of alkanes, with most of the recent research being focused on the functionalization of methane and light alkanes, where their selective transformation at reasonable conversions remains, even nowadays, an important challenge. In this review, we will cover the use of microporous zeolite-type materials as components of mono- and bifunctional catalysts in the catalytic activation and conversion of C1+ alkanes under non-oxidative or oxidative conditions. In each case, the alkane activation will be approached from a fundamental perspective, with the aim of understanding, at the molecular level, the role of the active sites involved in the activation and transformation of the different molecules and the contribution of shape-selective or confinement effects imposed by the microporous structure.Recent publications have suggested that oxidative DNA damage mediated by hydroxyl radical (˙OH) is unimportant in vivo, and that carbonate anion radical (CO3˙-) plays the key role. We examine these claims and summarize the evidence that ˙OH does play a key role as an important member of the reactive oxygen species (ROS) in vivo.A novel, compact and sensitive SE-LIAD/TOF-MS has been described. It facilitates fast sample preparation, and a full mass spectrum is acquired efficiently and sensitively. More importantly, it features the detection of non-acidic and non-basic or non-polar species, which is not suitable for determination by ESI and MALDI techniques. In this technique, standard samples, carbazole and melamine, are prepared on a Ti foil with a quartz plate attached to the backside of the Ti foil to perform a laser-induced acoustic desorption experiment (SE-LIAD) coupled to TOF-MS for analysis. Enhanced signals are observed with about 5.6 to 13.8 times higher than that obtained in the standard LIAD method, dependent on different ionization techniques. Compared to the EI spectra, the PI spectra for both species show intact and sharp molecular peaks. The limits of detection (LOD) of melamine were evaluated experimentally in the range from ∼2-6 pg (EI/MS mode) to ∼0.3-0.5 ng (VUV-SPI/MS mode). Thus, the method in this study exhibits rapid qualitative and quantitative analysis with good sensitivity, being free of the complex matrix influences.The electronic structure and photophysical properties of a series of N-methyl and N-acetyl substituted alloxazines (AZs) were investigated with extensive density functional theory (DFT) and time-dependent density functional theory (TD-DFT) based calculations. We showed that non-radiative decays from the lowest singlet and triplet excited states of these AZs are dominant over their radiative counterparts. The fast non-radiative decays of the excited AZs can be attributed to the energy consumption (Ereorg) through structural reorganization facilitated by the intrinsic normal modes of the alloxazine framework, as well as their coupling with those of the functional groups. Substitution with functional groups may lead to further perturbation of the electronic structure of the AZ chromophore, which may enhance intersystem crossing with the ππ* states of the AZs. Due to the different bonding of N1 and N3 within the alloxazine framework, substitution may result in AZs with different photophysical properties. Specifically, functionalization at N1 may help in maintaining or even reducing Ereorg and would promote the absorption and radiative decay from the excited AZs.
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