Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks

Introduction of hydrogen bond functionality into metal-organic frameworks can enhance guest binding and activation, but a combination of linker flexibility and interligand hydrogen bonding often results in the generation of unwanted structures where the functionality is masked. Herein, we describe the self-assembly of three materials, where Cd2+, Ca2+, and Zn2+ are linked by N,Nʹ-bis(4-carboxyphenyl)urea, and examine the effect of the urea units on structure formation, the generation of unusual secondary building units, structural flexibility, and guest binding. The flexibility of the Zn MOF is probed through single-crystal to single-crystal transformations upon exchange of DMF guests for CS2, showing that the lability of the [Zn4O(RCO2)6] cluster towards solvation enables the urea linkers to adopt distorted conformations as the MOF breathes, even facilitating rotation from the trans/trans to the trans/cis conformation without compromising the overall topology. The results have significant implications in the mechanistic understanding of the hydrolytic stability of MOFs, and in preparing heterogeneous organocatalysts

Relaxation phenomena of dithiolene type radical ligands for quantum computation

The intrinsic redox activity of the dithiolene ligand is used here as the novel spin host in a prototype molecular electron spin qubit where the traditional roles of the metal and ligand components in coordination complexes are inverted. A series of paramagnetic bis(dithiolene) complexes with group 10 metals– nickel, palladium, platinum – provides a backdrop to investigate the spin dynamics of the organic ligand radical using pulsed EPR spectroscopy. The temperature dependence of the phase memory time (TM) is shown to be dependent on the identity of the diamagnetic metal ion, with the short times recorded for platinum a consequence of a diminishing spin-lattice (T1) relaxation time driven by spin-orbit coupling. The utility of the radical ligand spin center is confirmed when it delivers one of the longest phase memory times ever recorded for a molecular two-qubit prototype. A bis(dithiolene)gold complex is presented as a model for an organic molecular electron spin qubit attached to a metallic surface that acts as a conduit to electrically address the qubit. A two-membered electron transfer series is developed of the formula [AuIII(adt)2]1–/0, where adt is a redox-active dithiolene ligand that is sequentially oxidized as the series is traversed while the central metal ion remains AuIII and steadfastly square planar. One-electron oxidation of diamagnetic [AuIII(adt)2]1– produces an S = 1/2 charge-neutral complex, [AuIII(adt)(adt•)] which is spectroscopically and theoretically characterized with a near negligible Au contribution to the ground state. A phase memory time (TM) of 21 μs is recorded in 4:1 CS2/CCl4 at 10 K, which is the longest ever reported for a coordination complex possessing a third-row transition metal ion. With increasing temperature, TM is dramatically decreased becoming unmeasurable above 80 K as a consequence of the diminishing spin-lattice (T1) relaxation time fuelled by spin-orbit coupling. These relaxation times are 1–2 orders of magnitude shorter for the solid dilution of in isoelectonic [Ni(adt)2] because this material is a molecular semiconductor. Although the conducting properties of this material provide efficient pathways to dissipate the energy through the lattice, it can also be used to electrically address the paramagnetic dopant by tapping into the mild reduction potential to switch magnetism “on” and “off” in the gold complex without compromising the integrity of its structure. These results serve to highlight the need to consider the composition of not just the qubit, but all components of these spintronic assemblies. Addition of Lewis acidic rare earth ions to the bis(dithiooxalato)nickel complex ion generated new charge-neutral heterometallic species where the rare earth M(III) ions (M = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) occupy the O,O′ pocket of both ligands. Together with stabilising hydrotris(pyrazolyl)borate co-ligands on the rare earth ion, chemical reduction of the bridging bis(dithiooxalato)nickel unit led to the first molecular and electronic structure characterisation of the elusive dithiooxalato radical ligand, (dto)3–• for the YIII and GdIII analogues. The central metal was varied down group 10 with lutetium to form a series with which to further investigate the environment of the radical spin

The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry

Reduction of 1,10-phenanthroline-5,6-dione (pd) with CoCpR2 resulted in the first molecular compounds of the pd˙− semi-quinone radical anion, [CoCpR2]+[pd]˙− (R = H, (1); R = Me4, (2)). Furthermore compounds 1 and 2 were reacted with [Y(hfac)3(thf)2] (hfac = 1,1,1-5,5,5-hexafluoroacetylacetonate) to synthesise the rare earth-transition metal heterometallic compounds, [CoCpR2]+[Y(hfac)3(N,N′-pd)]˙− (R = H, (3); R = Me4, (4))

The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N′ or O,O′ binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)3(N,N’-pd)] (Ln = Y [1], Gd [2]; hfac = hexafluoroacetylacetonate) were synthesised in high yield. These complexes have been fully characterised using a range of spectroscopic techniques. Solid state molecular structures of 1 and 2 have been determined by X-ray crystallography and display different pd binding modes in coordinating and non-coordinating solvents. Complexes 1 and 2 are unusually highly coloured in coordinating solvents, for example the vis-NIR spectrum of 1 in acetonitrile displays an electronic transition centred at 587 nm with an extinction coefficient consistent with significant charge transfer. The reaction between 1 and 2 and VCp2 or VCpt2 (Cpt = tetramethylcyclopentadienyl) resulted in the isolation of the heterobimetallic complexes, [Ln(hfac)3(N,N′-O,O′-pd)VCp2] (Ln = Y [3], Gd [4]) or [Ln(hfac)3(N,N′-O,O′-pd)VCpt2] (Ln = Y [5], Gd [6]). The solid state molecular structures of 3, 5 and 6 have been determined by X-ray crystallography. The spectroscopic data on 3–6 are consistent with oxidation of V(II) to V(IV) and reduction of pd to pd2− in the heterobimetallic complexes. The spin-Hamiltonian parameters from low temperature X-band EPR spectroscopy of 3 and 5 describe a 2A1 ground state, with a V(IV) centre. DFT calculations on 3 are in good agreement with experimental data and confirm the SOMO as the dx2−y2 orbital localised on vanadium

Enabling single qubit addressability in a molecular semiconductor comprising gold-supported organic radicals

A bis(dithiolene)gold complex is presented as a model for an organic molecular electron spin qubit attached to a metallic surface that acts as a conduit to electrically address the qubit. A two-membered electron transfer series is developed of the formula [AuIII(adt)2]1−/0, where adt is a redox-active dithiolene ligand that is sequentially oxidized as the series is traversed while the central metal ion remains AuIII and steadfastly square planar. One-electron oxidation of diamagnetic [AuIII(adt)2]1− (1) produces an S = 1/2 charge-neutral complex, [AuIII(adt23−˙)] (2) which is spectroscopically and theoretically characterized with a near negligible Au contribution to the ground state. A phase memory time (TM) of 21 μs is recorded in 4 : 1 CS2/CCl4 at 10 K, which is the longest ever reported for a coordination complex possessing a third-row transition metal ion. With increasing temperature, TM dramatically decreases becoming unmeasurable above 80 K as a consequence of the diminishing spin-lattice (T1) relaxation time fueled by spin–orbit coupling. These relaxation times are 1–2 orders of magnitude shorter for the solid dilution of 2 in isoelectronic [Ni(adt)2] because this material is a molecular semiconductor. Although the conducting properties of this material provide efficient pathways to dissipate the energy through the lattice, it can also be used to electrically address the paramagnetic dopant by tapping into the mild reduction potential to switch magnetism “on” and “off” in the gold complex without compromising the integrity of its structure. These results serve to highlight the need to consider all components of these spintronic assemblies

Ligand radicals as modular organic electron spin qubits

The intrinsic redox activity of the dithiolene ligand is presented here as the novel spin host in the design of prototype molecular electron spin qubit where the traditional roles of the metal and ligand components in coordination complexes are inverted. A series of paramagnetic bis(dithiolene) complexes with group 10 metals – nickel, palladium, platinum – provides a backdrop to investigate the spin dynamics of the organic ligand radical using pulsed EPR spectroscopy. The temperature dependence of the phase memory time (TM) is shown to be dependent on the identity of the diamagnetic metal ion with the short times recorded for platinum a consequence of a diminishing spin‐lattice (T1) relaxation time driven by spin‐orbit coupling. The utility of the radical ligand spin center is confirmed when it delivers one of the longest phase memory times ever recorded for a molecular two‐qubit prototype

Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination

Heterometallic rare earth transition metal compounds of dithioxalate (dto)2–, [NiII{(dto)LnIIITp2}2] (Ln = Y (1), Gd (2); Tp = hydrotris(pyrazol-1-yl)borate) were synthesised. The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[NiII{(dto)LnIIITp2}2]˙− Ln = Y (3), Gd (4). The reduction is ligand-based and 3 and 4 are the first examples of both molecular and electronic structural characterisation of the dithiooxalato radical (dto)3˙−

Computer vision for kinetic analysis of lab- and process-scale mixing phenomena

A software platform for the computer vision-enabled analysis of mixing phenomena of relevance to process scale-up is described. By bringing new and known time-resolved mixing metrics under one platform, hitherto unavailable comparisons of pixel-derived mixing metrics are exemplified across non-chemical and chemical processes. The analytical methods described are applicable using any camera and across an appreciable range of reactor scales, from development through to process scale-up. A case study in nucleophilic aromatic substitution run on 5L-scale shows how camera and offline concentration measurements can be correlated. In some cases, it can be shown that camera data holds the power to predict reaction progress

Teaching old presumptive tests new digital tricks with computer vision for forensic applications

Presumptive (or ‘spot’) tests have served forensic scientists, law enforcement, and legal practitioners for over a hundred years. Yet, the intended design of such tests, enabling quick identification of drugs by-eye, also hides their full potential. Here, we report the development and application of time-resolved imaging methods of reactions attending spot tests for amphetamines, barbiturates, and benzodiazepines. Analysis of the reaction videos helps distinguish drugs within the same structural class that, by-eye, are judged to give the same qualitative spot test result. It is envisaged that application of these results will bridge the existing suite of field and lab-based confirmatory forensic tests, and support a broader range of colorimetric sensing technologies

Molecular One- and Two-Qubit Systems with Very Long Coherence Times

General-purpose quantum computation and quantum simulation require multi-qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are promising materials for the realization of large-scale quantum architectures, due to their high degree of positionability and the possibility to precisely tailor interqubit interactions. The simplest quantum architecture is the two-qubit system, with which quantum gate operations can be implemented. To be viable, a two-qubit system must possess long coherence times, the interqubit interaction must be well defined and the two qubits must also be addressable individually within the same quantum manipulation sequence. Here results are presented on the investigation of the spin dynamics of chlorinated triphenylmethyl organic radicals, in particular the perchlorotriphenylmethyl (PTM) radical, a mono-functionalized PTM, and a biradical PTM dimer. Extraordinarily long ensemble coherence times up to 148 µs are found at all temperatures below 100 K. Two-qubit and, importantly, individual qubit addressability in the biradical system are demonstrated. These results underline the potential of molecular materials for the development of quantum architectures.The authors acknowledge the following funding: Center for Integrated Quantum Science and Technology, Carl Zeiss Foundation, Baden Württemberg Stiftung (QT5), Vector Foundation, Fonds der Chemischen Industrie. The work was also supported by Generalitat de Catalunya 2021 SGR 00443, MICINN (GENESIS PID2019-111682RB-I00), and the “Severo Ochoa” Programme for Centers of Excellence in R&D FUNFUTURE CEX2019-000917-S, CSIC Interdisciplinary Thematic Platform on Quantum Technologies (PTI QTEP+) (20219PT016, QTP2021-03-003). This research is part of the CSIC program for the Spanish Recovery, Transformation and Resilience Plan funded by the Recovery and Resilience Facility of the European Union, established by the Regulation (EU) 2020/2094. The authors further acknowledge financial support from EPSRC (UK) by funding the EPSRC National Research Facility for EPR spectroscopy at Manchester (NS/A000055/1; EP/W014521/1). The authors thank Yannick Thiebes for recording the powder X-ray diffractogram of Figure S15, Supporting Information.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).Peer reviewe