The electronic configuration of rare earth (RE) elements, characterised by their valence 4forbitals, results in unique magnetic, photophysical, and redox behaviour. These intrinsic attributes have allowed for the application of RE elements into an array of modern technologies, such as bio-imaging and light-emitting devices. These properties arise from the contracted 4f-orbitals leading to a strong spin-orbit perturbation on the electronic structure. Nevertheless, crystal field (CF) perturbation on the spin-orbit coupled J states has allowed for control over the RE 3+ electronic structure and hence overall features. As a result, strategic design/modulation of the coordination environment has become a powerful tool in fine-tuning and enhancing their properties, diversifying potential applications ranging from molecular magnets to catalysis. The point symmetry of the RE 3+ site and its influence on crystal field theory, play an important role in dictating allowed transitions between spin-orbit states in luminescent emissions, as well as mixing of CF states within ground J terms. For instance, understanding the effects of symmetry has allowed advancement of the research field of single-molecule magnets (SMMs), where discrete molecules retain magnetic memory. Three main relaxation regimes are present in zero-field SMMs: Orbach mechanism that is dictated by thermal relaxation over an energy barrier (Ueff), Raman relaxation induced by the simultaneous absorption and emission of two phonons, and the temperature independent quantum tunnelling of magnetization (QTM). High-order symmetry, such as D4d, inhibits all transverse mixing of wavefunctions, leading to pure CF states ultimately suppressing the rate-determining QTM regime. The significance of symmetry is stressed for SMMs that contain non-Kramer ions (even 4f electron counts) due to the lack of inherent bistability, with highest symmetries enforcing doubly degenerate states, as observed for odd-electron Kramers doublets (KD). In addition, symmetry has been an important factor in engineering entangled states in a phenomenon known as clock transitions due to selectively allowing mixing of CF states. For SMMs, the electrostatic model has been an important concept in developing highperforming SMMs. The largest mJ state can be approximated as oblate (e.g. Dy 3+ ) or prolate (e.g. Yb 3+ ) in shape, where stabilization can be achieved through the design of an axial or equatorial CF respectively yielding large Ueff. The electronic structure of RE ions becomes more intricate when introducing radical ligands. Notably, the best performing SMM to date, (Cp iPr5 )2Dy2I3 (Cp iPr5 = pentaisopropylcyclopentadiene), contains a radical localised in a σ-bonding orbital. The odioxolenes have been widely used in coordination chemistry due to accessibility in three oxidation states, the dianionic catecholate (cat 2-), monoanionic radical semiquinonate (SQ •-), and neutral quinonate (Q 0 ). The versatility is further enhanced by their amenability to chemical tuning via functionalization of the aromatic backbone allowing control of the ligands' electronic properties. For instance both electron-withdrawing and electron-donating groups have been incorporated into RE complexes. It is often necessary to employ a redox-inactive or a diamagnetic ancillary ligand to limit the number of redox-active sites, tune the CF perturbation, or enhance luminescence. While the RE 3+ elements typically exhibit weak luminescence due to forbidden f-f transitions between the 2S+1 LJ states, this can be enhanced through the antenna effect facilitating energy transfer from the excited ligand to metal centre. This process generally occurs in three steps: (1) excitation of the ligand singlet ground state to the lowest lying excited state, (2) intersystem crossing to the triplet state, (3) energy transfer to an excited spin-orbit state. In this study, we employ the tripodal tris(2pyridylmethyl)amine (tpa) ligand as it is known to sensitises RE luminescence. The fine structure of f-f emission bands can provide valuable insight into the CF splitting. This has been seen in metals such as Tb 3+ , Dy 3+ , and Yb 3+ , benefitting SMM studies and complementing ab initio calculations. Herein, we report the synthesis and characterization of a family of RE 3+ complexes [RE III (Br4catH)3(tpa)] (RE = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, Br4catH -= tetrabromocatecholate, tpa = tris(2-pyridylmethyl)amine) which crystallise in the R3c space group, facilitating the investigation of C3 molecular point symmetry on various physical properties for a variety of RE metals. The combination of structural, spectroscopic, electrochemical, magnetic, computational, and photophysical techniques were used to elucidate the electronic structure of both ligand and metal.