Spin-bearing molecules are promising building blocks for quantum technologies as they can be chemically tuned, assembled into scalable arrays, and readily incorporated into diverse device architectures. In molecular systems, optically addressing ground-state spins would enable a wide range of applications in quantum information science, as has been demonstrated for solid-state defects. However, this important functionality has remained elusive for molecules. Here, we demonstrate such optical addressability in a series of synthesized organometallic, chromium(IV) molecules. These compounds display a ground-state spin that can be initialized and read out using light, and coherently manipulated with microwaves. In addition, through atomistic modification of the molecular structure, we vary the spin and optical properties of these compounds, indicating promise for designer quantum systems synthesized from the bottom-up.

Synthetic chemistry enables a bottom-up approach to quantum information science, where atoms can be deterministically positioned in a quantum bit or qubit. Two key requirements to realize quantum technologies are qubit initialization and readout. By imbuing molecular spins with optical initialization and readout mechanisms, analogous to solid-state defects, molecules could be integrated into existing quantum infrastructure. To mimic the electronic structure of optically addressable defect sites, we designed the spin-triplet, V 3+ complex, (C 6 F 5 ) 3 trenVCN t Bu (1). We measured the static spin properties as well as the spin coherence time of 1 demonstrating coherent control of this spin qubit with a 240 GHz electron paramagnetic resonance spectrometer powered by a free electron laser. We found that 1 exhibited narrow, near-infrared photoluminescence (PL) from a spin-singlet excited state. Using variable magnetic field PL spectroscopy, we resolved emission into each of the ground-state spin sublevels, a crucial component for spin-selective optical initialization and readout. This work demonstrates that trigonally symmetric, heteroleptic V 3+ complexes are candidates for optical spin addressability.

The second quantum revolution hinges on the creation of materials that unite atomic structural precision with electronic and structural tunability. A molecular approach to quantum information science (QIS) promises to enable the bottom-up creation of quantum systems. Within the broad reach of QIS, which spans fields ranging from quantum computation to quantum communication, we will focus on quantum sensing. Quantum sensing harnesses quantum control to interrogate the world around us. A broadly applicable class of quantum sensors would feature adaptable environmental compatibility, control over distance from the target analyte, and a tunable energy range of interaction. Molecules enable customizable “designer” quantum sensors with tunable functionality and compatibility across a range of environments. These capabilities offer the potential to bring unmatched sensitivity and spatial resolution to address a wide range of sensing tasks from the characterization of dynamic biological processes to the detection of emergent phenomena in condensed matter. In this Outlook, we outline the concepts and design criteria central to quantum sensors and look toward the next generation of designer quantum sensors based on new classes of molecular sensors.

The inherent atomistic precision of synthetic chemistry enables bottom-up structural control over quantum bits, or qubits, for quantum technologies. Tuning paramagnetic molecular qubits that feature optical-spin initialization and readout is a crucial step toward designing bespoke qubits for applications in quantum sensing, networking, and computing. Here, we demonstrate that the electronic structure that enables optical-spin initialization and readout for S = 1, Cr(aryl) 4 , where aryl = 2,4dimethylphenyl (1), o-tolyl (2), and 2,3-dimethylphenyl (3), is readily translated into Cr(alkyl) 4 compounds, where alkyl = 2,2,2triphenylethyl (4), (trimethylsilyl)methyl ( 5), and cyclohexyl (6). The small ground state zero field splitting values (<5 GHz) for 1− 6 allowed for coherent spin manipulation at X-band microwave frequency, enabling temperature-, concentration-, and orientation-dependent investigations of the spin dynamics. Electronic absorption and emission spectroscopy confirmed the desired electronic structures for 4−6, which exhibit photoluminescence from 897 to 923 nm, while theoretical calculations elucidated the varied bonding interactions of the aryl and alkyl Cr 4+ compounds. The combined experimental and theoretical comparison of Cr(aryl) 4 and Cr(alkyl) 4 systems illustrates the impact of the ligand field on both the ground state spin structure and excited state manifold, laying the groundwork for the design of structurally precise optically addressable molecular qubits.