Creating the next generation of quantum systems requires control and tunability, which are key features of molecules. To design these systems, one must consider the ground-state and excited-state manifolds. One class of systems with promise for quantum sensing applications, which require water solubility, are d8 Ni2+ ions in octahedral symmetry. Yet, most Ni2+ complexes feature large zero-field splitting, precluding manipulation by commercial microwave sources due to the relatively large spin-orbit coupling constant of Ni2+ (630 cm-1). Since low lying excited states also influence axial zero-field splitting, D, a combination of strong field ligands and rigidly held octahedral symmetry can ameliorate these challenges. Towards these ends, we performed a theoretical and computational analysis of the electronic and magnetic structure of a molecular qubit, focusing on the impact of ligand field strength on D. Based on those results, we synthesized 1, [Ni(ttcn)2](BF4)2 (ttcn = 1,4,7-trithiacyclononane), which we computationally predict will have a small D (Dcalc = +1.15 cm-1). High-field high-frequency electron paramagnetic resonance (EPR) data yield spin Hamiltonian parameters: gx = 2.1018(15), gx = 2.1079(15), gx = 2.0964(14), D = +0.555(8) cm-1 and E = +0.072(5) cm-1, which confirm the expected weak zero-field splitting. Dilution of 1 in the diamagnetic Zn analogue, [Ni0.01Zn0.99(ttcn)2](BF4)2 (1') led to a slight increase in D to ∼0.9 cm-1. The design criteria in minimizing D in 1via combined computational and experimental methods demonstrates a path forward for EPR and optical addressability of a general class of S = 1 spins.
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