-
Herbert White posted an update 6 months ago
Organic chromophores with large Stokes shifts and dual emissions are fascinating because of their fundamental and applied interest. Tat-BECN1 molecular weight Vibration-induced emission (VIE) refers to a tunable multiple fluorescence exhibited by saddle-shaped N,N’-disubstituted-dihydribenzophenazines (DHPs), which involves photo-induced configuration vibrations from bent to planar form along the N-N axis. VIE-active molecules show intrinsic long-wavelength emissions in the unconstrained state (planar state) but bright short-wavelength emissions in the constrained state (bent state). The emission response for VIE-active luminogens is highly sensitive to steric hindrance encountered during the planarization process such that a tiny structural variation can induce an evident change in fluorescence. This can often be achieved by tuning the intensity ratio of short- and long-wavelength bands. In some special cases, the alterations in the emission wavelength of VIE fluorophores can be achieved step by step by harnessing the degree of bending angle motion in the excited state. In this perspective, we summarize the latest progress in the field of VIE research. New bent heterocyclic structures, as novel types of VIE molecules, are being developed, and the general features of the chemical structures are also being proposed. Technologically, novel emission color-tuning approaches and VIE-based probes for visualizing biological activity are presented to demonstrate how the dynamic VIE effect can be exploited for cutting-edge applications.We introduce a framework for the calculation of ground and excited state energies of bosonic systems suitable for near-term quantum devices and apply it to molecular vibrational anharmonic Hamiltonians. Our method supports generic reference modal bases and Hamiltonian representations, including the ones that are routinely used in classical vibrational structure calculations. We test different parametrizations of the vibrational wavefunction, which can be encoded in quantum hardware, based either on heuristic circuits or on the bosonic Unitary Coupled Cluster Ansatz. In particular, we define a novel compact heuristic circuit and demonstrate that it provides a good compromise in terms of circuit depth, optimization costs, and accuracy. We evaluate the requirements, number of qubits and circuit depth, for the calculation of vibrational energies on quantum hardware and compare them with state-of-the-art classical vibrational structure algorithms for molecules with up to seven atoms.We evaluate the effect of the number of methanol molecules per acidic site of H-ZSM-5 on the methoxylation reaction at room temperature by applying operando diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) and mass spectrometry (MS), which capture the methoxylation reaction by simultaneously probing surface adsorbed species and reaction products, respectively. To this end, the methanol loading in H-ZSM-5 (Si/Al ≈ 25) pores is systematically varied between 32, 16, 8 and 4 molecules per unit cell, which corresponds to 8, 4, 2 and 1 molecules per Brønsted acidic site, respectively. The operando DRIFTS/MS data show that the room temperature methoxylation depends on the methanol loading the higher the methanol loading, the faster the methoxylation. Accordingly, the reaction is more than an order of magnitude faster with 8 methanol molecules per Brønsted acidic site than that with 2 molecules, as evident from the evolution of the methyl rock band of the methoxy species and of water as a function of time. Significantly, no methoxylation is observed with ≤1 molecule per Brønsted acidic site. However, hydrogen bonded methanol occurs across all loadings studied, but the structure of hydrogen bonded methanol also depends on the loading. Methanol loading of ≤1 molecule per acidic site leads to the formation of hydrogen bonded methanol with no proton transfer (i.e. neutral geometry), while loading ≥2 molecules per acidic site results in a hydrogen bonded methanol with a net positive charge on the adduct (protonated geometry). The infrared vibrational frequencies of methoxy and hydrogen bonded methanol are corroborated by Density Functional Theory (DFT) calculations. Both the experiments and calculations reflect the methoxy bands at around 940, 1180, 2868-2876 and 2980-2973 cm-1 which correspond to ν(C-O), ρ(CH3), νs(C-H) and νas(C-H), respectively.In recent years, the development of sophisticated analytical tools, kinetic models and sample preparation methods has significantly advanced the field of supramolecular polymerization, where the competition of kinetic vs. thermodynamic processes has become commonplace for a wide range of building blocks. Typically, the kinetic pathways are identified in thermally controlled assembly experiments before they ultimately evolve to the thermodynamic minimum. However, there might be cases where the identification and thus the assessment of the influence of kinetic aggregates is not trivial, making the analysis of the self-assembly processes a hard task. Herein, we demonstrate that “hidden” kinetic pathways can have drastic consequences on supramolecular polymerization processes, to the point that they can even overrule thermodynamic implications. To this end, we analyzed in detail the supramolecular polymerization of a chiral PdII complex 1 that forms two competing aggregates (Agg I and Agg II) of which kinetic Agg II is formed through a “hidden” pathway, i.e. this pathway is not accessible by common thermal polymerization protocols. The hidden pathway exhibits two consecutive steps first, Agg II is formed in a cooperative process, which subsequently evolves to clustered superstructures driven by rapid kinetics. At standard conditions, Agg II displays an extraordinary kinetic stability (>6 months), which could be correlated to its cooperative mechanism suppressing nucleation of thermodynamic Agg I. Furthermore, the fast kinetics of cluster formation sequester monomers from the equilibria in solution and prevents the system from relaxing into the thermodynamic minimum, thus highlighting the key implications of hidden pathways in governing supramolecular polymerization processes.
Please follow & like us :)
All content contained on CatsWannaBeCats.Com, unless otherwise acknowledged,is the property of CatsWannaBeCats.Com and subject to copyright.