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Low-energy electrons dissolved in liquid ammonia or aqueous media are powerful reducing agents that promote challenging reduction reactions, but can also cause radiation damage to biological tissue. Knowledge of the underlying mechanistic processes remains incomplete, in particular with respect to the details and energetics of the electron transfer steps. Here, we show how ultraviolet (UV) photoexcitation of metal-ammonia clusters could be used to generate tunable low-energy electrons in situ. Specifically, we identified UV light-induced generation of spin-paired solvated dielectrons and their subsequent relaxation by an unconventional electron-transfer-mediated decay as an efficient low-energy electron source. The process is robust and straightforward to induce, with the prospect of improving our understanding of radiation damage and fostering mechanistic studies of solvated electron reduction reactions. 

Beryllium ammonia complexes Be(NH 3 ) 4 are known to bear two diffuse electrons in the periphery of a Be(NH 3 ) 4 2+ skeleton. The replacement of one ammonia with a methyl group forms CH 3 Be(NH 3 ) 3 with one peripheral electron, which is shown to maintain the hydrogenic-type shell model observed for Li(NH 3 ) 4 . Two CH 3 Be(NH 3 ) 3 monomers are together linked by aliphatic chains to form strongly bound beryllium ammonia complexes, (NH 3 ) 3 Be(CH 2 ) n Be(NH 3 ) 3 , n = 1–6, with one electron around each beryllium ammonia center. In the case of a linear carbon chain, this system can be seen as the analog of two hydrogen atoms approaching each other at specific distances (determined by n). We show that the two electrons occupy diffuse s-type orbitals and can couple exactly as in H 2 in either a triplet or singlet state. For long hydrocarbon chains, the singlet is an open-shell singlet nearly degenerate with the triplet spin state, which transforms to a closed-shell singlet for n = 1 imitating the σ-covalent bond of H 2 . The biradical character of the system is analyzed, and the singlet–triplet splitting is estimated as a function of n based on multi-reference calculations. Finally, we consider the case of bent hydrocarbon chains, which allows the closer proximity of the two diffuse electrons for larger chains and the formation of a direct covalent bond between the two diffuse electrons, which happens for two Li(NH 3 ) 4 complexes converting the open-shell to closed-shell singlets. The energy cost for bending the hydrocarbon chain is nearly compensated by the formation of the weak covalent bond rendering bent and linear structures nearly isoenergetic. 

Metal complexes with diffuse solvated electrons (solvated electron precursors) are proposed as alternative catalysts for the simultaneous CO 2 capture and utilization. Quantum chemical calculations were used to study the reaction of CO 2 with H 2 and C 2 H 4 to produce formic acid, methyldiol and δ-lactone. Mechanisms of a complete reaction pathway are found and activation barriers are reasonably low. The metal ligand complex readily reduces CO 2 and significantly stabilizes CO 2 ˙ − . Ligand identity minimally influences the reaction. Additional reactions and future strategies are proposed with the goal of inducing experimental interest. 

Abstract Density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery. Such complexes (solvated electron precursors or SEPs) have been experimentally identified and studied theoretically for several s- and d-block metals. For the first time, we demonstrate that a p-block metalloid element can form a stable SEP when appropriate ligands are chosen. We show that three ammonia and one methyl ligands can displace two of the three boron valence electrons to a peripheral 1s-type orbital. The shell model for these outer electrons is identical to previous SEP systems (1s, 1p, 1d, 2s). Further, we preformed the first examination of a molecular system consisting of two SEPs bridged by a hydrocarbon chain. The electronic structure of these dimers is very similar to that of traditional diatomic molecules forming bonding and anti-bonding σ and π orbitals. Their ground state electronic structure resembles that of two He atoms, and our results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer. These findings pave the way for the development of novel materials similar to expanded metals and electrides. 

High-level electronic structure calculations are carried out to obtain optimized geometries and excitation energies of neutral lithium, sodium, and potassium complexes with two ethylenediamine and one or two crown ether molecules. Three different sizes of crowns are employed (12-crown-4, 15-crown-5, 18-crown-6). The ground state of all complexes contains an electron in an s-type orbital. For the mono-crown ether complexes, this orbital is the polarized valence s-orbital of the metal, but for the other systems this orbital is a peripheral diffuse orbital. The nature of the low-lying electronic states is found to be different for each of these species. Specifically, the metal ethylenediamine complexes follow the previously discovered shell model of metal ammonia complexes (1s, 1p, 1d, 2s, 1f), but both mono- and sandwich di-crown ether complexes bear a different shell model partially due to their lower (cylindrical) symmetry and the stabilization of the 2s-type orbital. Li(15-crown-5) is the only complex with the metal in the middle of the crown ether and adopts closely the shell model of metal ammonia complexes. Our findings suggest that the electronic band structure of electrides (metal crown ether sandwich aggregates) and expanded metals (metal ammonia aggregates) should be different despite the similar nature of these systems (bearing diffuse electrons around a metal complex).