Evgeny V. Tretyakov

Ultrafast Photoswitching in a Copper‐Nitroxide‐Based Molecular Magnet

Molecular compounds with photoswitchable magnetic properties have been intensively investigated over the last decades due to their prospective applications in nanoelectronics, sensing and magnetic data storage. The family of copper-nitroxide-based molecular magnets represents a new promising type of photoswitchable compounds. We report the first study of these appealing systems using femtosecond optical spectroscopy. We unveil the mechanism of ultrafast (<50 fs) spin state photoswitching and establish its principal differences compared to other photoswitchable magnets. On this basis, we propose potential advantages of copper-nitroxide-based molecular magnets for the future design of ultrafast magnetic materials.

W-band time-resolved electron paramagnetic resonance study of light-induced spin dynamics in copper-nitroxide-based switchable molecular magnets.

Molecular magnets Cu(hfac)(2)L(R) represent a new type of photoswitchable materials based on exchange-coupled clusters of copper(II) with stable nitroxide radicals. It was found recently that the photoinduced spin state of these compounds is metastable on the time scale of hours at cryogenic temperatures, similar to the light-induced excited spin state trapping phenomenon well-known for many spin-crossover compounds. Our previous studies have shown that electron paramagnetic resonance (EPR) in continuous wave (CW) mode allows for studying the light-induced spin state conversion and relaxation in the Cu(hfac)(2)L(R) family. However, light-induced spin dynamics in these compounds has not been studied on the sub-second time scale so far. In this work we report the first time-resolved (TR) EPR study of light-induced spin state switching and relaxation in Cu(hfac)(2)L(R) with nanosecond temporal resolution. To enhance spectral resolution we used high-frequency TR EPR at W-band (94 GHz). We first discuss the peculiarities of applying TR EPR to the solid-phase compounds Cu(hfac)(2)L(R) at low (liquid helium) temperatures and approaches developed for photoswitching/relaxation studies. Then we analyze the kinetics of the excited spin state at T = 5-21 K. It has been found that the photoinduced spin state is formed at time delays shorter than 100 ns. It has also been found that the observed relaxation of the excited state is exponential on the nanosecond time scale, with the decay rate depending linearly on temperature. We propose and discuss possible mechanisms of these processes and correlate them with previously obtained CW EPR data.

Photoswitching of a Thermally Unswitchable Molecular Magnet Cu(hfac)2Li-Pr Evidenced by Steady-State and Time-Resolved Electron Paramagnetic Resonance

Most photoswitchable molecular magnets exhibit thermally induced switching, as is typical of spin crossover (SCO), valence tautomerism and SCO-like phenomena. We report a rare case of a copper-nitroxide based molecular magnet Cu(hfac)2L(i-Pr) that does not exhibit quantitative SCO-like behavior in the temperature range of its chemical stability (2-350 K); however, it can be switched to a metastable thermally inaccessible spin state via visible/near-IR light at cryogenic temperatures. By means of photogeneration, unique information on this otherwise unobservable spin state has been obtained using steady-state Q-band (34 GHz) and time-resolved W-band (94 GHz) electron paramagnetic resonance (EPR) spectroscopy. In particular, we have found that the electronic structure and relaxation properties of the photoinduced state in Cu(hfac)2L(i-Pr) are very similar to those in its sister compound Cu(hfac)2L(n-Pr) that is thermally switchable and has been exhaustively characterized by many analytical methods, previously. The first observation of photoswitchable behavior in a thermally unswitchable copper-nitroxide based molecular magnet Cu(hfac)2L(i-Pr) paves the way for photoswitching applications of this and similar compounds in the remarkably broad temperature range of 2-350 K.

Preparation and magnetic properties of metal-complexes from N-t-butyl-N-oxidanyl-2-amino-(nitronyl nitroxide).

Metal complexation reactions of N-t-butyl-N-oxidanyl-2-amino(nitronyl nitroxide) diradical (1) with M(hfac)2 (M: Mn or Cu) were investigated. These reactions were found to be very sensitive to the type of metal ion employed. Complex [Mn(hfac)2·1], consisting of Mn(hfac)2 and diradical 1, was readily prepared by mixing the components. However, the reaction of Cu(hfac)2 with 1 or N-t-butyl-N-oxidanyl-2-amino(iminonitroxide) diradical (2) involved the reduction of the diradical to the N-t-butyl-N-oxidanide-2-amino(iminonitroxide) radical anion (3) and finally produced the polymer-chain complex [Cu2(hfac)2·32·Cu(hfac)2]n. The structures of these complexes were elucidated by X-ray analysis, and their magnetic properties were investigated in detail. The temperature dependence of χpT (χp: magnetic susceptibility) for [Mn(hfac)2·1] exhibited a strong antiferromagnetic interaction (H = -2JS1·S2, J/kB = -217 K) between the Mn(II) spin (S = 5/2) and the diradical 1 spin (S = 1). However, the χpT-T plots for [Cu2(hfac)2·32·Cu(hfac)2]n indicated the presence of several magnetic interactions: a large ferromagnetic interaction (J/kB = 510 K) between iminonitroxide 3 and the imino-coordinating Cu(II) atom, a moderately large ferromagnetic interaction (J/kB = 58 K) between the iminonitroxide and (iminonitroxide oxygen)-coordinating Cu(hfac)2, and a weak antiferromagnetic interaction (J/kB = -1.4 K) between the two Cu(hfac)-3 moieties within a Cu2O2 square.

Crucial Role of Paramagnetic Ligands for Magnetostructural Anomalies in “Breathing Crystals”

Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals. Contrary to that, their structural analogues with diamagnetic ligands do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and copper(II) ions for the origin of magnetostructural anomalies in this family of molecular magnets.

C(sp2)‐Coupled Nitronyl Nitroxide and Iminonitroxide Diradicals

Spin-labelled compounds are widely used in chemistry, physics, biology and the materials sciences but the synthesis of stable high-spin organic molecules is still a challenge. We succeeded in synthesising heteroatom analogues of the 1,1,2,3,3-pentamethylenepropane (PMP) diradicals with two nitronyl nitroxide (DR1) and with two iminonitroxide (DR2) fragments linked through the C(sp2) atom of the nitrone group. According to magnetic susceptibility measurements, EPR data and ab initio calculations at the (8,6)CASSCF and (8,6)NEVPT2 levels, DR1 and DR2 have singlet ground states. The singlet–triplet energy splitting (2J) is low (J/k=−7.4 for DR1 and −6.0 K for DR2), which comes from the disjoint nature of these diradicals. The reaction of [Cu(hfac)2] with DR1 gives rise to different heterospin complexes in which the diradical acts as a rigid ligand, retaining its initial conformation. For the [{Cu(hfac)2}2(DR1)(H2O)] complex, sufficiently strong ferromagnetic interactions (J1/k=42.7 and J2/k=14.1 K) between two coordinating CuII ions and DR1 were revealed. In [{Cu(hfac)2}2(DR1)(H2O)][Cu(hfac)2(H2O)], the very strong and antiferromagnetic (J/k=−416.1 K) exchange interaction between one of the coordinating CuII ions and DR1 is caused by the very short equatorial CuO bond length (1.962 Å).

Trityl-based alkoxyamines as NMP controllers and spin-labels

Recently, new applications of trityl-nitroxide biradicals were proposed. In the present study, attachment of a trityl radical to alkoxyamines was performed for the first time. The rate constants kd of C-ON bond homolysis in these alkoxyamines were measured and found to be equal to those for alkoxyamines without trityl. The electron paramagnetic resonance (EPR) spectra of the products of alkoxyamine homolysis (trityl-TEMPO and trityl-SG1 biradicals) were recorded, and the corresponding exchange interactions were estimated. The decomposition of trityl-alkoxyamine showed more than an 80% yield of biradicals, meaning that the C-ON bond homolysis is the main reaction. The suitability of these labelled initiators/controllers for polymerisation was exemplified by means of successful nitroxide-mediated polymerisation (NMP) of styrene. Thus, this is the first report of a spin-labelled alkoxyamine suitable for NMP.

Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (1) lithium derivative was found to react with perfluorobenzonitrile (2) substituting its para-fluorine atom to form 2-(4-cyanotetrafluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (3), a new nitronyl nitroxide containing a multifunctional framework of strong electron-withdrawing nature. This result shows the possibility of obtaining multifunctional nitronyl nitroxides via the interaction of paramagnetic lithium derivatives as C-nucleophiles with polyfluoroarenes activated for nucleophilic substitution. The reaction regioselectivity is supported by the data of quantum-chemical calculations, which also show that the reaction follows a concerted pathway without formation of an intermediate. Reduction of nitronyl nitroxide 3 in system NaNO2-AcOH yielded corresponding iminonitroxide 4. Characterization of persistent radicals 3 and 4 obtained by the SNF synthetic strategy includes X-ray crystal structures, electron spin resonance data, and static magnetic-susceptibility measurements. X-ray diffraction analysis of both nitronyl nitroxide and iminonitroxide revealed a complete match of the parameters of their crystal lattices.

Reaction of Paramagnetic Synthon, Lithiated 4,4,5,5-Tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide, with Cyclic Aldonitrones of the Imidazole Series

It was shown that dipole-stabilized paramagnetic carbanion lithiated 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide can be attached in a nucleophilic manner to either isolated or conjugated aldonitrones of the 2,5-dihydroimidazole 3-oxide and 2H-imidazole 1-oxide series to afford adducts the subsequent oxidation of which leads to polyfunctional mono- and diradicals. According to XRD, at least two polymorphic modifications can be formed during crystallization of the resulting paramagnetic compounds, and for each of them, geometric parameters of the molecules are similar. An EPR spectrum of the diradical in frozen toluene has a complicated lineshape, which can be fairly well reproduced by using X-ray diffraction structural analysis and the following set of parameters: D=14.9 mT, E=1.7 mT; tensor a((14) N)=[0.260 0.260 1.625] mT, two equivalent tensors for the nitronyl nitroxide moiety a((14) N)=[0.198 0.198 0.700] mT, and g≈2.007. According to our DFT and ab initio calculations, the intramolecular exchange in the diradical is very weak and most likely ferromagnetic.

Cu(hfac)2 Complexes with Nitronyl Ketones Structurally Mimicking Nitronyl Nitroxides in Breathing Crystals

Breathing crystals based on polymer-chain complexes of Cu(hfac)2 (hfac = hexafluoroacetylacetonate) with nitronyl nitroxides represent a new type of molecular magnetic sensors, exhibiting thermally and light-induced structural rearrangements in the spin clusters Cu ← (O∸N<)n accompanied by magnetic anomalies. To shed light on the driving forces of the rearrangements a method for the synthesis of sterically hindered 4-oxo-3,4-dihydro-2H-pyrrole-N-oxides (nitronyl ketones) structurally mimicking nitronyl nitroxides in breathing crystals has been determined. This method employs palladium-catalyzed cross-coupling of 3,3,4-trimethyl-4-nitropentanoic acid chloride with 4-stannylpyrazoles, leading to the formation of nitroketones followed by soft reduction into hydroxylamines, that then undergo self-initiated cyclization into the corresponding nitrones. The radical oxidation of the latter finally yields the target nitronyl ketones. An X-ray diffraction analysis of the nitronyl ketones confirms that their structural characteristics are close to those of the corresponding nitronyl nitroxides. Moreover, upon reaction with Cu(hfac)2, diamagnetic nitronyl ketones form polymer-chain complexes with a ‘head-to-tail’ motif and a structure similar to their analogues containing paramagnetic nitronyl nitroxides. Finally, it has been found that one of the complexes with nitronyl ketones does manifest a purely structural phase transition similar to its copper-nitroxide analogue, but at the same time it does not manifest any signs of a magneto-structural transition characteristic for breathing crystals where a Jahn–Teller axis in the coordination units CuNO4(O∸N<) is flipped. This observation strongly confirms the crucial role of the exchange interactions between spins of copper and nitroxide for the origin of magneto-structural anomalies in breathing crystals.