Zimmerman Yildirim (maracapump6)

Coordination compounds, characterized by fascinating and tunable electronic properties, are capable of binding easily to proteins, polymers, wires and DNA. Upon irradiation, these molecular systems develop functions finding applications in solar cells, photocatalysis, luminescent and conformational probes, electron transfer triggers and diagnostic or therapeutic tools. The control of these functions is activated by the light wavelength, the metal/ligand cooperation and the environment within the first picoseconds (ps). After a brief summary of the theoretical background, this perspective reviews case studies, from 1st row to 3rd row transition metal complexes, that illustrate how spin-orbit, vibronic coupling and quantum effects drive the photophysics of this class of molecules at the early stage of the photoinduced elementary processes within the fs-ps time scale range.This tutorial review focuses on the valorisation of biomass by sonochemical and mechanochemical activation. Although several of the examples reported herein rely on the use of model compounds rather than native feedstocks, the conversion of lignocellulosic fractions into valuable compounds is a great opportunity with which to more sustainably exploit natural resources, from environmental, economic and social points of view. The use of non-conventional technologies that generate high-energy microenvironments can improve biomass deconstruction and the accessibility of catalysts, granting higher conversion and selectivity. The critical parameters in sonochemical and mechanochemical conversions have been analysed together with the most common devices and reactors, and the potential of sonocatalysis and mechanocatalysis as emerging tools for both catalytic and biocatalytic biomass conversion will be discussed. A SWOT (strengths, weaknesses, opportunities and threats) analysis will provide an overview of the effective feasibility of these approaches in a biorefinery context. Although these technologies offer indisputable advantages (mild reaction conditions, enhanced reaction rates and mass transfer), their mechanisms and the systematic adjustment of parameters to give optimal outcomes still require further investigation, which will pave the way for reproducible and scalable experiments. Indeed, process scale-up can be accomplished both in batch and flow mode. However, results are not particularly predictable, despite the accurate control of instrumental variables, because of the variability found in biomass sources and the complexity inherent in structures.An organobase assisted approach is adopted to synthesize a series of β-ketoenamine-linked covalent organic frameworks (COFs), exhibiting superior crystallinity and porosity in comparison with those using an acidic catalyst. The quality promotion arises from the organobase-modulated transimination that favors the reaction kinetics for self-improvement of ordered structures.The synthetic utility of aryl radicals has been established in the last century, however, their broad applications were hampered by ineffective generation methods. It was in the last decade, that a rapid development of various redox systems took place, thus triggering a renaissance of aryl radical chemistry. This tutorial review focuses on the start-of-the-art methods for generation of aryl radicals. Primarily, various light-induced systems, including photoredox catalysis, visible light transition metal catalysis, and chemistry of electron donor-acceptor complexes, are reviewed. The main current precursors of aryl radicals are evaluated together with the selected examples of their modern applications.We benchmark the accuracy of quantum-chemical methods, including wave function theory methods [coupled cluster theory at the CCSD(T) level, multiconfigurational perturbation-theory (CASPT2, NEVPT2) and internally contracted multireference configuration interaction (MRCI)] and 30 density functional theory (DFT) approximations, in reproducing the spi