Near-term decarbonization of aviation requires energy-dense, renewable liquid fuels. Biomass-derived 1,4-dimethylcyclooctane (DMCO), a cyclic alkane with a volumetric net heat of combustion up to 9.2% higher than Jet A, has the potential to serve as a low-carbon, high-performance jet fuel blendstock that may enable paraffinic bio-jet fuels to operate without aromatic compounds. DMCO can be produced from bio-derived isoprenol (3-methyl-3-buten-1-ol) through a multistep upgrading process. This study presents detailed process configurations for DMCO production to estimate the minimum selling price and life-cycle greenhouse gas (GHG) footprint considering three different hydrogenation catalysts and two bioconversion pathways. The platinum-based catalyst offers the lowest production cost and GHG footprint of $9.0/L-Jet-Aeq and 61.4 gCO2e/MJ, given the current state of technology. However, when the supply chain and process are optimized, hydrogenation with a Raney nickel catalyst is preferable, resulting in a $1.5/L-Jet-Aeq cost and 18.3 gCO2e/MJ GHG footprint if biomass sorghum is the feedstock. This price point requires dramatic improvements, including 28 metric-ton/ha sorghum yield and 95-98% of the theoretical maximum conversion of biomass-to-sugars, sugars-to-isoprenol, isoprenol-to-isoprene, and isoprene-to-DMCO. Because increased gravimetric energy density of jet fuels translates to reduced aircraft weight, DMCO also has the potential to improve aircraft efficiency, particularly on long-haul flights.

A series of dysprosium(iii) metallocenium salts, [Dy(Cp^iPr4R)₂][B(C₆F₅)₄] (R = H (1), Me (2), Et (3), iPr (4)), was synthesized by reaction of DyI₃ with the corresponding known NaCp^iPr4R (R = H, iPr) and novel NaCp^iPr4R (R = Me, Et) salts at high temperature, followed by iodide abstraction with [H(SiEt₃)₂][B(C₆F₅)₄]. Variation of the substituents in this series results in substantial changes in molecular structure, with more sterically-encumbering cyclopentadienyl ligands promoting longer Dy-C distances and larger Cp-Dy-Cp angles. Dc and ac magnetic susceptibility data reveal that these structural changes have a considerable impact on the magnetic relaxation behavior and operating temperature of each compound. In particular, the magnetic relaxation barrier increases as the Dy-C distance decreases and the Cp-Dy-Cp angle increases. An overall 45 K increase in the magnetic blocking temperature is observed across the series, with compounds 2-4 exhibiting the highest 100 s blocking temperatures yet reported for a single-molecule magnet. Compound 2 possesses the highest operating temperature of the series with a 100 s blocking temperature of 62 K. Concomitant increases in the effective relaxation barrier and the maximum magnetic hysteresis temperature are observed, with 2 displaying a barrier of 1468 cm^-1 and open magnetic hysteresis as high as 72 K at a sweep rate of 3.1 mT s^-1. Magneto-structural correlations are discussed with the goal of guiding the synthesis of future high operating temperature Dy^III metallocenium single-molecule magnets.

The recent discovery of metal-metal bonding and valence delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4fn5dz21 electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (CpiPr5)3Ln3H3I2 (1-Ln, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (CpiPr5)3Ln3H3I3. Structural, computational, and spectroscopic analyses support valence delocalization in 1-Ln resulting from a three-center, one-electron σ bond formed from the 4dz2 and 5dz2 orbitals on Y and Gd, respectively. Dc magnetic susceptibility data obtained for 1-Gd reveal that valence delocalization engenders strong parallel alignment of the σ-bonding electron and the 4f electrons of each gadolinium center to afford a high-spin ground state of S = 11. Notably, this represents the first clear instance of metal-metal bonding in a molecular trilanthanide complex, and the large spin-spin exchange constant of J = 168(1) cm-1 determined for 1-Gd is only the second largest coupling constant characterized to date for a molecular lanthanide compound.