Slow Electron Spin Relaxation at Ambient Temperatures with Copper Coordinated by a Rigid Macrocyclic Ligand

Abstract

Paramagnetic transition metal complexes can serve as quantum bits, storing phase information through unpaired electrons. Despite their promise, these systems often require low temperatures and tend to rapidly decohere. Recent efforts have sought to improve longitudinal relaxation (T1), which provides an upper limit for phase coherence (Tm), by investigating existing literature compounds with reduced vibrational coupling and orbital angular momentum. However, synthetic strategies for improving T1 through novel ligand design have remained scant. Here, we disclose the synthesis of a new modular macrocyclic ligand framework with four nitrogen donors (N4) derived from phenanthroline that supports room-temperature coherent Cu(II) spin centers. The optimized complex more than doubles the T1 over the next best Cu(II)-N4 compound and exhibits a room temperature coherence time (Tm) of 0.28 μs, close to previously reported values. This performance enhancement arises from a tight binding site with short Cu-N distances, resulting in a stronger ligand field and reduced thermal accessibility of symmetric vibrational modes. This work demonstrates a practical approach to enabling spin coherence at room temperature, a factor critical to accessing relevant quantum bits and biological sensors, through a designer macrocyclic ligand platform.