Atomic-Scale Quantum Sensing of Ensembles of Guest Molecules in a Metal–Organic Framework with Intrinsic Electron Spin Centers

Kultaeva, Anastasia; Pöppl, Andreas; Biktagirov, Timur

doi:10.1021/acs.jpclett.2c01429

Cited by 10 publications

(8 citation statements)

References 45 publications

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“…Two critical performance metrics of coherence times are (i) the spin–lattice ( T 1 ) and (ii) spin–spin relaxation ( T 2 ) times, which describe the timescale for maintaining the arbitrary superposition and phase coherence of quantum states, respectively . Previous studies performed on metal–organic frameworks (MOFs) indicate that varying the spatial relationship between qubit centers allows for the systematic tuning of the T 1 and T 2 relaxation times. ,,− Recently, MOF-based spin qubits have enabled quantum sensing of molecules and ions in the MOF pores. − However, MOFs derive their periodicity from coordination bonds to metal ions, which sometimes possess unpaired d -electrons and/or impart strong spin-orbit coupling that interfere with coherence of the electronic spin qubits. These influences might be suppressed in all-organic systems that contain no d -electrons and exhibit negligible spin-orbit coupling.…”

Section: Introductionmentioning

confidence: 99%

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers

et al. 2022

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Molecular electronic spin qubits are promising candidates for quantum information science applications because they can be reliably produced and engineered via chemical design. Embedding electronic spin qubits within two-dimensional polymers (2DPs) offers the possibility to systematically engineer inter-qubit interactions while maintaining long coherence times, both of which are prerequisites to their technological utility. Here, we introduce electronic spin qubits into a diamagnetic 2DP by n-doping naphthalene diimide subunits with varying amounts of CoCp 2 and analyze their spin densities by quantitative electronic paramagnetic resonance spectroscopy. Low spin densities (e.g., 6.0 × 10 12 spins mm −3 ) enable lengthy spin−lattice (T 1 ) and spin−spin relaxation (T 2 ) times across a range of temperatures, ranging from T 1 values of 164 ms at 10 K to 30.2 μs at 296 K and T 2 values of 2.36 μs at 10 K to 0.49 μs at 296 K for the lowest spin density sample examined. Higher spin densities and temperatures were both found to diminish T 1 times, which we attribute to detrimental cross-relaxation from spin− spin dipolar interactions and spin−phonon coupling, respectively. Higher spin densities decreased T 2 times and modulated the T 2 temperature dependence. We attribute these differences to the competition between hyperfine and dipolar interactions for electron spin decoherence, with the dominant interaction transitioning from the former to the latter as spin density and temperature increase. Overall, this investigation demonstrates that dispersing electronic spin qubits within layered 2DPs enables chemical control of their inter-qubit interactions and spin decoherence times.

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Section: Introductionmentioning

confidence: 99%

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers

et al. 2022

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“…Aiming at the realization of functions targeted construction of MOF, the porous features of the framework could be utilized to introduce specific guest species (small molecules, coordination compounds, polymers, etc.) for function modulation. − Accordingly, the host–guest method has developed as a highly effective and straightforward way for the functionalization of MOF. − By following this strategy, we have developed a series of highly functional MOFs by introducing donor–acceptor (D–A) interactions into the MOF system through the host–guest manner. − Generally, by using an electron-deficient 2,4,6-tri(4-pyridinyl)-1,3,5-triazine (TPT)-based linker as the acceptor for the construction of host MOF, electron-rich guests (polyaromatic hydrocarbons, PAHs) could be introduced into the framework as a donor to accomplish the D–A system (Scheme top). In addition to the synergy of D–A interaction and coordination interaction that could modulate the structure of the D–A MOF, the guest donor-dependent highly tunable intrinsic photoluminescent properties of the D–A systems could be effectively transferred to the host–guest MOF .…”

Section: Introductionmentioning

confidence: 99%

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

et al. 2023

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Metal−organic frameworks (MOFs) have been recognized as a potential platform for the development of tunable luminophores owing to their highly modulable structures and components. Herein, two MOF luminophores based on Cd(II) ions, 1,3,5-tri(4-pyridinyl)benzene (TPB), and 1,4-dicarboxybenzene (H 2 BDC) were constructed. The directed assembly of the metal ions and organic linkers results in [Cd 2 (BDC) 2 (TPB)(H 2 O)]•x(solvent) (MOF-1) featuring TPB-based blue fluorescence centered at 425 nm. By introducing anthracene as the structure directing agent (SDA) for assembly regulation, [Cd 2 (BDC)-(TPB) 2 (NO 3 ) 2 ]•x(solvent) (MOF-2) was obtained, which reveals anthracene feeding-dependent high tunable emission in the 517−650 nm range. Detailed components, photophysical properties, and structural characteristics investigations of MOF-2 indicate the TPB and NO 3 − interactions as the origin of its redshifted emission compared with that of MOF-1. Furthermore, the fluorescence of MOF-2 was found to be regulatable by the anthracene feeding based on the SDA-determined crystallinity of the crystalline sample. All these results provided a unique example of the structural and fluorescence regulation of MOF luminophores.

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“…MOFs are porous ordered solids composed of inorganic and organic molecular building blocks . They typically contain nanoscale or subnanoscale pores that have enabled their use in traditional sensing applications. , Previously, it has been shown that electron spins in microporous zeolites and MOFs can be used to detect guest species by hyperfine spectroscopy, but these demonstrations were performed at cryogenic temperatures (below 10 K) due to the limitation of electron spin coherence and/or sensitivity. − Here, we seek to incorporate organic radicals into the MOF backbone to enable room-temperature operability while preserving pore accessibility, leading to close radical–analyte contacts through adsorption (Figure b). In addition, MOFs can be elaborated as inert and insoluble solids for either liquid or solution phase analytes (Figure a).…”

Section: Introductionmentioning

confidence: 99%

Room-Temperature Quantitative Quantum Sensing of Lithium Ions with a Radical-Embedded Metal–Organic Framework

et al. 2022

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Recent advancements in quantum sensing have sparked transformative detection technologies with high sensitivity, precision, and spatial resolution. Owing to their atomic-level tunability, molecular qubits and ensembles thereof are promising candidates for sensing chemical analytes. Here, we show quantum sensing of lithium ions in solution at room temperature with an ensemble of organic radicals integrated in a microporous metal–organic framework (MOF). The organic radicals exhibit electron spin coherence and microwave addressability at room temperature, thus behaving as qubits. The high surface area of the MOF promotes accessibility of the guest analytes to the organic qubits, enabling unambiguous identification of lithium ions and quantitative measurement of their concentration through relaxometric and hyperfine spectroscopic methods based on electron paramagnetic resonance (EPR) spectroscopy. The sensing principle presented in this work is applicable to other metal ions with nonzero nuclear spin.

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Atomic-Scale Quantum Sensing of Ensembles of Guest Molecules in a Metal–Organic Framework with Intrinsic Electron Spin Centers

Cited by 10 publications

References 45 publications

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

Room-Temperature Quantitative Quantum Sensing of Lithium Ions with a Radical-Embedded Metal–Organic Framework

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