We have described the synthesis and properties of nine new symmetrically and asymmetrically arylated pentalenides, including a strategy for the introduction of alkyl substituents with β-hydrogens that otherwise lead to exocyclic deprotonation. The di-alkali metal salts crystallise in the usual trans η 5 coordination mode, but in ethereal solution solvent-separated ion pairs exist that feature rapid (likely concerted) substituent flipping. High-level DFT calculations have confirmed a dihedral twist angle of ~30° (as found experimentally in the solid state) as the energetic minimum due to steric clash competing with the electronic preference for co-planar conjugation. Even at a 30° twist versus the pentalenide core, four aryl substituents have been shown to withdraw over 50% of the charge density from the core and reduce its aromaticity by up to 20%. The NMR chemical shifts of the wingtip protons in the 2,5-positions on the pentalenide core serve as sensitive probes for the polarisation, charge density and degree of aromaticity of the two five-membered subunits of the pentalenide core, and the C NMR shifts of the quaternary carbons connected to the aryl substituents are related to the dihedral angle and degree of conjugation. Whereas unsubstituted C8H6 2-is best described as a fully conjugated sp 2 system containing 10 π electrons around its perimeter (with negligible electron density at its transannular bond), when aryls are introduced in the 1,3,4,6 positions conjugation with the substituents leads to charge localisations in these pentalenides that are more accurately depicted as two allyl units fused together by a C=C bond. Frontier orbital analysis has shown such arylated pentalenides to be slightly weaker donors (i.e. less reducing) but much better acceptor ligands than unsubstituted (and likely also alkylated) pentalenides, making them promising "soft" ligands for electron-rich metal centres. After spending the past 60 years as something of a sleeping beauty, the ease and modularity of our synthetic protocol paired with the quantum chemical insights reported here will hopefully enable more widespread utilisation of this ligand framework and finally allow its full potential in organometallic chemistry to be realised. In particular, the possibility of designing electronically asymmetric pentalenide ligands offers exciting prospects for the controlled synthesis of homo-and heterobimetallic complexes for application in sensing, functional materials and catalysis. Further variations in substitution patterns, including multiple alkyl groups introduced via complementary strategies, as well as their use in organometallic chemistry will be reported in due course.