The transformative applications of quantum information science (QIS) require precise design and integration of networks of qubits, the fundamental units of QIS systems. Chemical synthesis is a powerful approach, offering routes to modular, atomically precise arrangements of identical qubits. Herein, we employed the versatility of framework chemistry to investigate spin and lattice dynamics of the expanded copper(II) porphyrinic framework Zr−Cu−NU-1102 (2) possessing Cu−Cu distances of 18.0 Å. Pulse electron paramagnetic resonance spectroscopy revealed a significant reduction in relaxation processes mediated by qubit−qubit interactions compared with the more spin-dense Cu−PCN-224 (1) framework. With the reduction in the spin−spin relaxation process, phonon-mediated processes emerged as the primary driver of spin−lattice relaxation. We synthesized the isoreticular Hf−Cu−NU-1102 (3) to elucidate the impact of the nodes versus the ligands on the phonon-mediated relaxation process. Measurement of 3 revealed identical spin−lattice relaxation dynamics to 2, thereby excluding involvement of node-centered or bulk framework acoustic modes. Supported by theoretical calculations of the ligand vibrational modes, these results implicated linker-based motions as dominant contributors to phonon-mediated spin−lattice relaxation. These findings provide clear guidelines for synthetic design to control spin and phonon interactions in modular arrays of molecular qubits.

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.

Regioselective carbyne-transfer reagents derived from (3,3,3-trifluoroprop-1-yn-1-yl)benzene give access to functionalized ring-opening alkyne metathesis polymerization (ROAMP) initiators [R-CHC≡Mo(OC(CH)(CF))] featuring electron-donating or -withdrawing substituents on the benzylidyne. Kinetic studies and linear free-energy relationships reveal that the initiation step of the ring-opening alkyne metathesis polymerization of 5,6,11,12-tetradehydrobenzo[a,e][8]annulene exhibits a moderate positive Hammett reaction constant (ρ = +0.36). ROAMP catalysts featuring electron-withdrawing benzylidynes not only selectively increase the rate of initiation (k) over the rate of propagation (k) but also prevent undesired intra- and intermolecular chain-transfer processes, giving access to linear poly-(o-phenylene ethynylene) with narrow molecular weight distribution. The regioselective carbyne transfer methodology and the detailed mechanistic insight enabled the design of a bifunctional ROAMP-reversible addition-fragmentation chain-transfer (RAFT) initiator complex. ROAMP followed by RAFT polymerization yields hybrid poly-(o-phenylene ethynylene)-block-poly-(methyl acrylate) block copolymers.

The combination of structural precision and reproducibility of synthetic chemistry is perfectly suited for the creation of chemical qubits, the core units of a quantum information science (QIS) system. By exploiting the atomistic control inherent to synthetic chemistry, we address a fundamental question of how the spin−spin distance between two qubits impacts electronic spin coherence. To achieve this goal, we designed a series of molecules featuring two spectrally distinct qubits, an early transition metal, Ti 3+ , and a late transition metal, Cu 2+ with increasing separation between the two metals. Crucially, we also synthesized the monometallic congeners to serve as controls. The spectral separation between the two metals enables us to probe each metal individually in the bimetallic species and compare it with the monometallic control samples. Across a range of 1.2−2.5 nm, we find that electron spins have a negligible effect on coherence times, a finding we attribute to the distinct resonance frequencies. Coherence times are governed, instead, by the distance to nuclear spins on the other qubit's ligand framework. This finding offers guidance for the design of spectrally addressable molecular qubits.

Molybdenum carbyne complexes [RC≡Mo(OC(CH3)(CF3)2)3] featuring a mesityl (R = Mes) or an ethyl (R = Et) substituent initiate the living ring-opening alkyne metathesis polymerization of the strained cyclic alkyne, 5,6,11,12-tetradehydrobenzo[a,e][8]annulene, to yield fully conjugated poly(o-phenylene ethynylene). The difference in the steric demand of the polymer end-group (Mes vs Et) transferred during the initiation step determines the topology of the resulting polymer chain. While [MesC≡Mo(OC(CH3)(CF3)2)3] exclusively yields linear poly(o-phenylene ethynylene), polymerization initiated by [EtC≡Mo(OC(CH3)(CF3)2)3] results in cyclic polymers ranging in size from n = 5 to 20 monomer units. Kinetic studies reveal that the propagating species emerging from [EtC≡Mo(OC(CH3)(CF3)2)3] undergoes a highly selective intramolecular backbiting into the butynyl end-group.

Atomically precise bottom-up synthesized graphene nanoribbons (GNRs) are promising candidates for next-generation electronic materials. The incorporation of these highly tunable semiconductors into complex device architectures requires the development of synthetic tools that provide control over the absolute length, the sequence, and the end-groups of GNRs. Here, we report the living chaingrowth synthesis of chevron-type GNRs (cGNRs) templated by a poly-(arylene ethynylene) precursor prepared through ring-opening alkyne metathesis polymerization (ROAMP). The strained triple bonds of a macrocyclic monomer serve both as the site of polymerization and the reaction center for an annulation reaction that laterally extends the conjugated backbone to give cGNRs with predetermined lengths and endgroups. The structural control provided by a living polymer-templated synthesis of GNRs paves the way for their future integration into hierarchical assemblies, sequence-defined heterojunctions, and well-defined single-GNR transistors via block copolymer templates.

Alkyne cross-metathesis of molybdenum carbyne complex [TolC≡Mo(OCCH(CF))]·DME with 2 equiv of functional ynamines or ynamides yields the primary cross-metathesis product with high regioselectivity (>98%) along with a molybdenum metallacyclobutadiene complex. NMR and X-ray crystal structure analysis reveals that ynamides derived from 1-(phenylethynyl)pyrrolidin-2-one selectively cleave the propagating molybdenum species in the ring-opening alkyne metathesis polymerization (ROAMP) of ring-strained 3,8-dihexyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e][8]annulene and irreversibly deactivate the diamagnetic molybdenum metallacyclobutadiene complex through a multidentate chelate binding mode. The chain termination of living ROAMP with substituted ethynylpyrrolidin-2-ones selectively transfers a functional end-group to the polymer chain, giving access to telechelic polymers. This regioselective carbyne transfer strategy gives access to amphiphilic block copolymers through synthetic cascades of ROAMP followed by ring-opening polymerization of strained ε-caprolactone.

Nanoscale graphene can be designed to function as a molecular qubit