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This work will offer new insights into COF-based probes and inspire the development of more versatile tools for biomedical applications.Multidimensional conical intersection seam has been characterized by utilizing the dynamic resonances in the nonadiabatic transition probability experimentally observed in the predissociation of thioanisole isotopomers. Cabotegravir The nonadiabatic bifurcation behavior of the reactive flux into either the Herzberg type-I (electronic) or type-II (vibrational) predissociation pathway is found to be strongly dependent on the quantum nature of the S1/S2 vibronic eigenstate, providing the essential information about structure and dynamic character of the conical intersection seam projected onto the normal mode space. By modifying the nature of the normal mode space through partial or full H/D substitution of the molecule, multiple aspects of the conical intersection seam could be characterized from different viewpoints set by the adjusted normal mode space. Theoretical calculations of potential energy curves along selected normal mode displacements support the experiment.It is known that the electrical conductance of single molecules can be controlled in a deterministic manner by chemically varying their anchor groups to external electrodes. Here, by employing synthetic methodologies to vary the terminal anchor groups around aromatic anthracene cores, and by forming self-assembled monolayers (SAMs) of the resulting molecules, we demonstrate that this method of control can be translated into cross-plane SAM-on-gold molecular films. The cross-plane conductance of SAMs formed from anthracene-based molecules with four different combinations of anchors are measured to differ by a factor of approximately 3 in agreement with theoretical predictions. We also demonstrate that the Seebeck coefficient of such films can be boosted by more than an order of magnitude by an appropriate choice of anchor groups and that both positive and negative Seebeck coefficients can be realised. This demonstration that the thermoelectric properties of SAMs are controlled by their anchor groups represents a critical step towards functional ultra-thin-film devices for future molecular-scale electronics.A highly diastereoselective dearomatization of naphthalenes via a Pd-catalyzed 1,4-difunctionalization reaction is described. In the presence of a commercially available palladium precursor and ligand, intramolecular dearomative Heck-type insertion provides π-allylpalladium intermediates which are readily captured by a series of nucleophiles in excellent yields (up to 99%). This reaction features mild conditions, broad substrate scope, and useful transformations of the products.Fluorescent probes are commonly used in studying G protein-coupled receptors in living cells; however their application to the whole animal receptor imaging is still challenging. To address this problem, we report the design and the synthesis of the first near-infrared emitting fluorogenic dimer with environment-sensitive folding. Due to the formation of non-fluorescent H-aggregates in an aqueous medium, the near-infrared fluorogenic dimer displays a strong turn-on response (up to 140-fold) in an apolar environment and exceptional brightness 56% quantum yield and ≈444 000 M-1 cm-1 extinction coefficient. Cabotegravir Grafted on a ligand of the oxytocin receptor, it allows the unprecedented background-free and target-specific imaging of the naturally expressed receptor in living mice.Obtaining transparent glasses made of functional coordination polymers (CPs) represents a tremendous opportunity for optical applications. In this context, the first transparent and red-emissive glasses of gold thiolate CPs have been obtained by simply applying mechanical pressure to amorphous powders of CPs. The three gold-based CP glasses are composed of either thiophenolate [Au(SPh)] n , phenylmethanethiolate [Au(SMePh)] n or phenylethanethiolate [Au(SEtPh)] n . The presence of a longer alkyl chain between the thiolate and the phenyl ring led to the formation of glass with higher transparency. The glass transitions, measured by thermomechanical analysis (TMA), occurred at lower temperature for CPs with longer alkyl chains. In addition, all three gold thiolate glasses exhibit red emission at 93 K and one of them, [Au(SMePh)] n , remains luminescent even at room temperature. An in-depth structural study of the amorphous gold thiolates by XRD, PDF and EXAFS analysis showed that they are formed of disordered doubly interpenetrated helical chains. These d10 metal-based compounds represent the first examples of transparent and luminescent CP glasses.A computer program for retrosynthetic planning helps develop multiple "synthetic contingency" plans for hydroxychloroquine and also routes leading to remdesivir, both promising but yet unproven medications against COVID-19. These plans are designed to navigate, as much as possible, around known and patented routes and to commence from inexpensive and diverse starting materials, so as to ensure supply in case of anticipated market shortages of commonly used substrates. Looking beyond the current COVID-19 pandemic, development of similar contingency syntheses is advocated for other already-approved medications, in case such medications become urgently needed in mass quantities to face other public-health emergencies.Yttrium is present in various forms in molecular compounds and solid-state structures; it typically provides specific mechanical and optical properties. Hence, yttrium containing compounds are used in a broad range of applications such as catalysis, lasers and optical devices. Obtaining descriptors that can provide access to a detailed structure-property relationship would therefore be a strong base for the rational design of such applications. Towards this goal, 89Y (100% abundant spin ½ nucleus), is associated with a broad range of NMR chemical shifts that greatly depend on the coordination environment of Y, rendering 89Y NMR an attractive method for the characterization of yttrium containing compounds. However, to date, it has been difficult to obtain a direct relationship between 89Y chemical shifts and its coordination environment. Here, we use computational chemistry to model the chemical shift of a broad range of Y(iii) molecular compounds with the goal to reveal the underlying factors that determine the 89Y chemical shift.
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