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Through a combination of X-ray and neutron total scattering and Empirical Potential Structure Refinement (EPSR) we explore the prenucleation structures of saturated aqueous magnesium sulfate. The atomistic model we present reveals a system characterised by isolated octahedral aquo magnesium species Mg(H2O)6, magnesium sulfate pairs (Mg(H2O)5SO4) and extended clusters built from corner-sharing MgO6 and SO4 polyhedra. Many of these features are directly observed in the crystal structures of the known solid form hydrates, including isolated polyhedra, corner sharing chains and rings, and it is only for the extended 3D polyhedral networks of the lower hydrates (mono- & di-) that no proto structures are observed in 2M solution. Looking at the average first solvation shell of the sulfate anion we see a complex and flexible environment that commonly includes water molecules brought into proximity by a coordinated hydrated magnesium. What emerges is a high probability that 10 water molecules will be observed in a combined tetrahedral/octahedral arrangement with a further 7 taking up more dispersed positions giving an average coordination of 17. The tendency for ions to aggregate into clusters allows areas of bulk water to exist that exhibit subtle differences in structure to that of pure water.

p class="Abstract"span lang="EN-GB"Herein, we present a highly diastereoselective method to furnish acyclic 3-amino-1,5-diol derivatives using a tandem double-aldol-Tishchenko protocol (italicdr/italicup togt;99:1) using a butanone derived sulfinylimine. In most cases only 1 diastereomer predominates, from a possible 16. The reaction is also regioselective. In addition, the highly challenging cyclobutanone and 3-pentanone derivatives are also amenable to a double-aldol-Tishchenko reaction, although theitalicdr/italicvalues are modest. Despite that, clean single diastereoisomers can be isolated, which should prove very useful in medicinal chemistry and other areas. Detailed DFT calculations support the observed stereoselectivities in all cases, providing a rationale for the excellentitalicdr/italicvalues in the butanone series and the moderate values for the 3-pentanone class.o:p/o:p/span/p.

The reaction of 2,6-diformyl-4-methylphenyl disulfide with [Ni(tn)3]Cl2 (tn = 1,3-diaminopropane), in methanol and in the presence of NaBPh4 resulted in the isolation of [Ni2(L1)](DMF)2(BPh4)2 (I), (L1 = 15,95-dimethyl-3,7,11,15-tetraaza-1,9(1,3)-dibenzenacyclohexadecaphane-2,7,10,15-tetraene-12,92-bis(thiolate). This reaction represents a 2-electron solvent assisted reduction of the disulfide bond to form two thiolate ligands where methanol is converted to formaldehyde and the two nickel centres remained in the + 2 oxidation state. The crystal structure of I showed the two nickel(II) atoms are bridged by two thiolates in a binuclear Ni2S2 core inside of a macrocyclic framework. The IR spectrum showed a band at 1625 cm−1, assigned to the imine ν(C [dbnd]N) stretch of the macrocyclic ligand, and bands at 734, 706 cm−1, are assigned to the tetraphenylborate counter ions. This is the first example of solvent assisted S–S bond cleavage being used to prepare a dicompartmental macrocyclic complex.

Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of

Ninhydrin bis-acetals give access to 8-ring lactones, benzocyclo-butenes and spirocyclic orthoanhydrides through photoextrusion and tandem photoextrusion reactions. Syntheses of fimbricalyxlactone B, isoshihunine and numerous biologically-relevant heterocycles show the value of the methods, while TA-spectroscopy and TD-DFT studies provide mechanistic insights on their wavelength dependence.

Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of m CB-Eu y Tb 1-y (y = 0-1) MOFs using a highly hydrophobic ligand mCBL1: 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane. The new materials are stable in water and at high temperature. Tunable emission from green to red, energy transfer (ET) from Tb3+ to Eu3+, and time-dependent emission of the series of mixed-metal m CB-Eu y Tb 1-y MOFs are reported. An outstanding increase in the quantum yield (QY) of 239% of mCB-Eu (20.5%) in the mixed mCB-Eu0.1Tb0.9 (69.2%) is achieved, along with an increased and tunable lifetime luminescence (from about 0.5 to 10 000 μs), all of these promoted by a highly effective ET process. The observed time-dependent emission (and color), in addition to the high QY, provides a simple method for designing high-security anticounterfeiting materials. We report a convenient method to prepare mixed-metal Eu/Tb coordination polymers (CPs) that are printable from water inks for potential applications, among which anticounterfeiting and bar-coding have been selected as a proof-of-concept., This work was financially supported by the MINECO (PID2019-106832RB-I00), MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (CEX2019-000917-S, MDM-2017-0767, and SEV-2017-0706 projects), grant RTI2018-098027-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe and the Generalitat de Catalunya (2017/SGR/1720 and SGR2017-1289). Z.L. is enrolled in the UAB Ph.D. program and acknowledges the China Scholarship Council (CSC) for his Ph.D. grant (201808310071)., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).