Metal-Metal Cooperation in the Oxidation of a Flapping Platinum Butterfly by Haloforms: Experimental and Theoretical Evidence

The model 1-DFT for the butterfly complex [{Pt(C¿C*)(µ-pz)}2] (1; HC¿C* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene) shows two minima in the potential energy surface of the ground state in acetone solution: the butterfly-wing-spreading molecules 1-s, (dPt-Pt ˜ 3.20 Å) and the wing-folding molecules 1-f (dPt-Pt = 3.00 Å). Both minima are very close in energy (¿G° = 1.7 kcal/mol) and are connected through a transition state, which lies only 1.9 kcal/mol above 1-s and 0.2 kcal/mol above 1-f. These very low barriers support a fast interconversion process, resembling a butterfly flapping, and the presence of both conformers in acetone solution. However, the 1-f ratio is so low that it is undetectable in the excitation and emission spectra of 1 in 2-MeTHF of diluted solutions (10-5 M) at 77 K, while it is seen in more concentrated solutions (10-3 M). In acetone solution, 1 undergoes a [2c, 2e] oxidation by CHX3 (X = Cl, Br) in the sunlight to render the Pt2(III, III) compounds [{Pt(C¿C*)(µ-pz)X)}2] (X = Cl (2-Cl), Br (2-Br)). In concentrated solutions, 1 can react with CHCl3 under blue light to give 2-Cl and with CHBr3 in the dark, the latter rendering the compound [BrPt(C¿C*)(µ-pz)2Pt(C¿C*)CHBr2] (3-Br) or mixtures of 2-Br and 3-Br if the reaction is performed under an argon atmosphere or in the air, respectively. Mechanistic studies showed that in concentrated solutions the oxidation processes follow a radical mechanism being the MMLCT-based species 1-f, those which trigger the reaction of 1 with CHBr3 and CHCl3. In the ground state (S0f), it promotes the thermal oxidation of 1 by CHBr3 and in the first singlet excited state (S1f) the blue-light-driven photooxidation of 1 by CHCl3. Complexes, 2-Cl, 2-Br, and 3-Br were selectively obtained and fully characterized, showing Pt-Pt distances (ca. 2.6 Å) shorter than that of the starting complex, 1. They are, together with the analogous [{Pt(C¿C*)(µ-pz)I)}2] and [IPt(C¿C*)(µ-pz)2Pt(C¿C*)CHI2], the only dinuclear metal-metal-bonded PtIII(µ-pz)2PtIII compounds reported to date

The socio-economic, dwelling and appliance related factors affecting electricity consumption in domestic buildings

This paper aims to investigate the socio-economic, dwelling and appliance related factors that have significant or non-significant effects on domestic electricity consumption. To achieve this aim, a comprehensive literature review of international research investigating these factors was undertaken. Although papers examining the factors affecting electricity demand are numerous, to the authors' knowledge, a comprehensive analysis taking stock of all previous findings has not previously been undertaken. The review establishes that no less than 62 factors potentially have an effect on domestic electricity use. This includes 13 socio-economic factors, 12 dwelling factors and 37 appliance factors. Of the 62 factors, four of the socio-economic factors, seven of the dwelling factors, and nine of the appliance related factors were found to unambiguously have a significant positive effect on electricity use. This paper contributes to a better understanding of those factors that certainly affect electricity consumption and those for which effects are unclear and require further research. Understanding the effects of factors can support both the implementation of effective energy policy and aid prediction of future electricity consumption in the domestic sector

Reversible Tuning of Ca Nanoparticles Embedded in a Superionic CaF2 Matrix

ABSTRACT: Controlling the size and shape of metallic colloids is crucial for a number of nanotechnological applications ranging from medical diagnosis to electronics. Yet, achieving tunability of morphological changes at the nanoscale is technically difficult and the structural modifications made on nanoparticles generally are irreversible. Here, we present a simple non-chemical method for controlling the size of metallic colloids in a reversible manner. Our strategy consists on applying hydrostatic pressure on a Ca cationic sublattice embedded in the irradiated matrix of CaF2 containing a large concentration of defects. Application of our method to CaF2 along with in situ optical absorption of the Ca plasmon shows that the radii of the Ca nanoparticles can be reduced with an almost constant rate of −1.2 nm/GPa up to a threshold pressure of ∼ 9.4 GPa. We demonstrate recovery of the original nanoparticles upon decompression of the irradiated matrix. The mechanisms for reversible nanocolloid-size variation are analyzed with first-principles simulations. We show that a pressure-driven increase in the binding energy between fluorine centers is responsible for the observed nanoparticle shrinkage. We argue that the same method can be used to generate other metallic colloids (Li, K, Sr, and Cs) with tailored dimensions by simply selecting an appropriate matrix

High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study

Complexes {Pt(C^C*)(µ-pz)}2] (HC^C*A= 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene 1a, HC^C*B= 1-phenyl-3-methyl-1H-imidazol-2-ylidene 1b) react with methyl iodide (MeI) at room temperature in the dark to give compounds {PtIV(C^C*)Me(µ-pz)}2(µ-I)]I (C^C*A2a, C^C*B2b). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded Br(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Bn] (5a), which by heating in BnBr(l) became {PtIV(C^C*A)Bn(µ-pz)}2(µ-Br)]Br (6a). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a SN2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as (C^C*A)PtIII(µ-pz)2PtIII(C^C*A)R]X (RX = MeI Int-Me, BnBr Int-Bn) and (C^C*A)PtII(µ-pz)2PtIV(C^C*A)(R)X] (RX = MeI Int'-Me, BnBr Int'-Bn) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as (C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me]BF4(3a') and used to get I(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me](4a), (C^C*A)PtII(µ-pz)2PtIV(C^C*A)(Me)I](Int'-Me), and {PtIV(C^C*)Me(µ-pz)}2(µ-I)]BF4(2a'). The single-crystal X-ray structures of 2a, 2b, 3a', and 5a along with the mono- and bi-dimensional 1H and 195Pt{1H} NMR spectra of all the named species allowed us to compare structural and spectroscopic data for high-valent complexes with the same core {Pt(C^C*)(µ-pz)}2] but different oxidation states. © 2022 American Chemical Society. All rights reserved

New analysis method for continuous base-flow and availability of water resources based on Parallel Linear Reservoir models

Water flows in the hydrosphere through a tangled and tortuous labyrinth of ways that is the hydrological cycle. Flow separation models are an attempt to group such complexity of paths into a few components of flow and storage so as to reflect the overall behaviour of a basin. A new method of analysis and separation of flow components, based on equations of dynamic relations between Linear Reservoirs connected in Parallel (PLR models), is developed in this article. A synthesis of models based on mathematical filter equations is carried out in order to make comparisons with the proposed model. Reference is also made to the methodology of adjustment and calibration of the PLR models based on the recession curves of the real hydrographs. The models are tested with the continuous register of a basin located in the northeast of Spain. The simulations are carried out with two reservoir models (2R models), three reservoirs (3R models) and with a mathematical filter model to compare the results. With the results of the models, flow duration curves (FDCs) and storage duration curves (SDCs) were elaborated, thus allowing assessment of the origin of the water resources of the basin, a guarantee of their regulation and availability, the dynamic storage in the catchment, residence times and other features

The actual performance of aspiring low energy social houses in the United Kingdom

This paper compares the actual energy performance of six flats and two houses built to low energy standards (Code for Sustainable Homes Levels 4 and 5) with a near identical flat and house built to minimum compliance only (Building Regulations). As low energy homes are only recently emerging in the United Kingdom housing stock, and even fewer are subject to Post Occupancy Evaluation, little is known about their actual energy use in operation. The results show that low energy dwellings may consume more energy than expected and the behaviour of the occupants residing in low energy homes plays an important role in determining their actual energy consumption

Entanglement spectra of critical and near-critical systems in one dimension

The entanglement spectrum of a pure state of a bipartite system is the full set of eigenvalues of the reduced density matrix obtained from tracing out one part. Such spectra are known in several cases to contain important information beyond that in the entanglement entropy. This paper studies the entanglement spectrum for a variety of critical and near-critical quantum lattice models in one dimension, chiefly by the iTEBD numerical method, which enables both integrable and non-integrable models to be studied. We find that the distribution of eigenvalues in the entanglement spectra agrees with an approximate result derived by Calabrese and Lefevre to an accuracy of a few percent for all models studied. This result applies whether the correlation length is intrinsic or generated by the finite matrix size accessible in iTEBD. For the transverse Ising model, the known exact results for the entanglement spectrum are used to confirm the validity of the iTEBD approach. For more general models, no exact result is available but the iTEBD results directly test the hypothesis that all moments of the reduced density matrix are determined by a single parameter.Comment: 6 pages, 5 figure