Observation of a molecular bond between ions and Rydberg atoms.

Atoms with a highly excited electron, called Rydberg atoms, can form unusual types of molecular bonds1-4. The bonds differ from the well-known ionic and covalent bonds5,6 not only by their binding mechanisms, but also by their bond lengths ranging up to several micrometres. Here we observe a new type of molecular ion based on the interaction between the ionic charge and a flipping-induced dipole of a Rydberg atom with a bond length of several micrometres. We measure the vibrational spectrum and spatially resolve the bond length and the angular alignment of the molecule using a high-resolution ion microscope7. As a consequence of the large bond length, the molecular dynamics is extremely slow. These results pave the way for future studies of spatio-temporal effects in molecular dynamics (for example, beyond Born-Oppenheimer physics).

Biochemical and Transcriptome Analysis Reveals Pigment Biosynthesis Influenced Chlorina Leaf Formation in Anoectochilus roxburghii (Wall.) Lindl.

Anoectochilus roxburghii (Wall.) Lindl is a perennial herb of the Orchidaceae family; a yellow-green mutant and a yellow mutant were obtained from the wild type, thereby providing good material for the study of leaf color variation. Pigment content analysis revealed that chlorophyll, carotenoids, and anthocyanin were lower in the yellow-green and yellow mutants than in the wild type. Transcriptome analysis of the yellow mutant and wild type revealed that 78,712 unigenes were obtained, and 599 differentially expressed genes (120 upregulated and 479 downregulated) were identified. Using the Kyoto Encyclopedia of Genes and Genomes pathway analysis, candidate genes involved in the anthocyanin biosynthetic pathway (five unigenes) and the chlorophyll metabolic pathway (two unigenes) were identified. Meanwhile, the low expression of the chlorophyll and anthocyanin biosynthetic genes resulted in the absence of chlorophylls and anthocyanins in the yellow mutant. This study provides a basis for similar research in other closely related species.

Psychological Health of Surgeons in a Time of COVID-19: A Global Survey.

OBJECTIVE: To assess the degree of psychological impact among surgical providers during the COVID-19 pandemic. SUMMARY OF BACKGROUND DATA: The COVID-19 pandemic has extensively impacted global healthcare systems. We hypothesized that the degree of psychological impact would be higher for surgical providers deployed for COVID-19 work, certain surgical specialties, and for those who knew of someone diagnosed with, or who died, of COVID-19. METHODS: We conducted a global web-based survey to investigate the psychological impact of COVID-19. The primary outcomes were the depression anxiety stress scale-21 and Impact of Event Scale-Revised scores. RESULTS: A total of 4283 participants from 101 countries responded. 32.8%, 30.8%, 25.9%, and 24.0% screened positive for depression, anxiety, stress, and PTSD respectively. Respondents who knew someone who died of COVID-19 were more likely to screen positive for depression, anxiety, stress, and PTSD (OR 1.3, 1.6, 1.4, 1.7 respectively, all P < 0.05). Respondents who knew of someone diagnosed with COVID-19 were more likely to screen positive for depression, stress, and PTSD (OR 1.2, 1.2, and 1.3 respectively, all P < 0.05). Surgical specialties that operated in the head and neck region had higher psychological distress among its surgeons. Deployment for COVID- 19-related work was not associated with increased psychological distress. CONCLUSIONS: The COVID-19 pandemic may have a mental health legacy outlasting its course. The long-term impact of this ongoing traumatic event underscores the importance of longitudinal mental health care for healthcare personnel, with particular attention to those who know of someone diagnosed with, or who died of COVID-19.

Observation of Vibrational Dynamics of Orientated Rydberg-Atom-Ion Molecules.

Vibrational dynamics in conventional molecules usually takes place on a timescale of picoseconds or shorter. A striking exception are ultralong-range Rydberg molecules, for which dynamics is dramatically slowed down as a consequence of the huge bond length of up to several micrometers. Here, we report on the direct observation of vibrational dynamics of a recently observed Rydberg-atom-ion molecule. By applying a weak external electric field of a few millivolts per centimeter, we are able to control the orientation of the photoassociated ultralong-range Rydberg molecules and induce vibrational dynamics by quenching the electric field. A high resolution ion microscope allows us to detect the molecule's orientation and its temporal vibrational dynamics in real space. Our study opens the door to the control of molecular dynamics in Rydberg molecules.

Alkyl Chains Modulated Magnetization Dynamics of Mononuclear Trigonal Prismatic CoII Complexes.

Four benzeneboron-capped mononuclear CoII complexes with different alkyl substitutions on the fourth position of phenylboronic acid were obtained. The CoII ions are all wrapped by the pocket-like ligands and located in trigonal prismatic coordination geometries. Alternating-current magnetic susceptibility measurements reveal that they show different magnetization dynamics, such as distinct relaxation rates at the same temperature, the faster QTM rates for the ethyl and propyl substituted complexes, as well as different relaxation processes. Magneto-structural correlation study reveals that the various deviations of coordination geometry of CoII ion, diverse crystal packings and possible different vibration modes of substituents caused by modifying alkyl chains are the key factors affecting the magnetization dynamics. This work demonstrates that the alkyl chains even locating far away from the metal center can have a large impact on the magnetic behavior of the CoII complex with a very rigid coordination geometry, offering a new perspective towards transition metal based single-molecule magnets.

Ligand Modulation of the Structures and Magnetic Relaxation in Triangular Dy3 Complexes Based on a Tricompartmental Scaffold.

Using a novel tricompartmental hydrazone ligand, a set of trinuclear Dy3 complexes has been isolated and structurally characterized. Complexes Dy3 ⋅ Cl, Dy3 ⋅ Br, and Dy3 ⋅ ClO4 feature a similar overall topology but different anions (Cl- , Br- , or ClO4 - ) in combination with exogenous OH- and solvent co-ligands, which is found to translate into very different magnetic properties. Complex Dy3 ⋅ Cl shows a double relaxation process with fast quantum tunneling of the magnetization, probably related to the structural disorder of µ2 -OH- and µ2 -Cl- co-ligands. Relaxation of the magnetization is slowed down for Dy3 ⋅ Br and Dy3 ⋅ ClO4 , which do not show any structural disorder. In particular, fast quantum tunneling is suppressed in case of Dy3 ⋅ ClO4 , resulting in an energy barrier of 341 K and magnetic hysteresis up to 3.5 K; this makes Dy3 ⋅ ClO4 one of the most robust air-stable trinuclear SMMs. Magneto-structural relationships of the three complexes are analyzed and rationalized with the help of CASSCF/RASSI-SO calculations.

Regulating Magnetic Relaxations of Cyano-Bridged {DyIII MoV } Systems by Tuning the N-Sites in ß-Diketone Ligands.

Cyano-bridged 4d-4f molecular nanomagnets have re-called increasing research interests in molecular magnetism since they offer more possibilities in achieving novel nanomagnets with versatile structures and magnetic interactions. In this work, four ß-diketone ligands bearing different substitution N-sites were designed and synthesized, namely 1-(2-pyridyl)-3-(3-pyridyl)-1,3-propanedione (HL1 ), 1,3-Bis (3-pyridyl)-1,3-propanedione (HL2 ), 1-(4-pyridyl)-3-(3-pyridyl)-1,3-propanedione (HL3 ), and 1,3-Bis (4-pyridyl)-1,3-propanedione (HL4 ), to tune the magnetic relaxation behaviors of cyano-bridged {DyIII MoV } systems. By reacting with DyCl3 ⋅ 6H2 O and K4 Mo(CN)8 ⋅ 2H2 O, four cyano-bridged complexes, namely {[Dy[MoV (CN)8 ](HL1 )2 (H2 O)3 ]} ⋅ 6H2 O (1), {[Dy[MoV (CN)8 ](HL2 )(H2 O)3 (CH3 OH)]}2 ⋅ 2CH3 OH ⋅ 3H2 O (2), {[Dy[MoV (CN)8 ](HL3 )(H2 O)2 (CH3 OH)] ⋅ H2 O}n (3), and {[Dy[MoV (CN)8 ](HL4 )2 (H2 O)3 ]} ⋅ 2H2 O⋅CH3 OH (4) were obtained. Structural analyses revealed that 1 and 4 are binuclear complexes, 2 has a tetragonal structure, and 3 exhibits a stair-like polymer chain structure. The DyIII ions in all complexes have eight-coordinated configurations with the coordination spheres DyO7 N1 for 1 and 4, DyO6 N2 for 2, and DyO5 N3 for 3. Magnetic measurements indicate that 1 is a zero-field single-molecule magnet (SMM) and complexes 2-4 are field-induced SMMs, with complex 4 featuring a two-step relaxation process. The magnetic characterizations and ab initio calculations revealed that changing the N-sites in the ß-diketone ligands can effectively alter the structures and magnetic properties of cyano-bridged 4d-4f nanomagnets by adjusting the coordination environments of the DyIII centers.

X-Ray Triggered Coordination-Bond Breakage in Dysprosium-Organic Framework and its Impact on Magnetic Properties.

Photosensitive lanthanide-based single-molecule magnets (Ln-SMM) are very attractive for their potential applications in information storage, switching, and sensors. However, the light-driven structural transformation in Ln-SMMs hardly changes the coordination number of the lanthanide ion. Herein, for the first time it is reported that X-ray (λ=0.71073 Å) irradiation can break the coordination bond of Dy-OH2 in the three-dimensional (3D) metal-organic framework Dy2 (amp2 H2 )3 (H2 O)6 ⋅ 4H2 O (MDAF-5), in which the {Dy2 (OPO)2 } dimers are cross-linked by dianthracene-phosphonate ligands. The structural transformation proceeds in a single-crystal-to-single-crystal (SC-SC) fashion, forming the new phase Dy2 (amp2 H2 )3 (H2 O)4 ⋅ 4H2 O (MDAF-5-X). The phase transition is accompanied by a significant change in magnetic properties due to the alteration in coordination geometry of the DyIII ion from a distorted pentagonal bipyramid in MDAF-5 to a distorted octahedron in MDAF-5-X.

Photocontrollable Magnetism and Photoluminescence in a Binuclear Dysprosium Anthracene Complex.

By incorporating photoreactive anthracene moieties into binuclear Dy2O2 motifs, we obtain two new compounds with the formulas [Dy2(SCN)4(L)2(dmpma)4] (1) and [Dy2(SCN)4(L)2(dmpma)2(CH3CN)2] (2), where HL is 4-methyl-2,6-dimethoxyphenol and dmpma is dimethylphosphonomethylanthracene. Compound 1 contains face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4 + 4] photocycloaddition reaction, while stacking of the anthracene groups in compound 2 does not meet the Schmidt rule. Compound 1 undergoes a reversible single-crystal-to-single-crystal structural transformation upon UV-light irradiation and thermal annealing, forming a one-dimensional coordination polymer of [Dy2(SCN)4(L)2(dmpma)2(dmpma2)]n (1UV). The process is concomitant with changes in the magnetic dynamics and photoluminescent properties. The spin-reversal energy barrier is significantly increased from 1 (55.9 K) to 1UV (116 K), and the emission color is changed from bright yellow for 1 to weak blue for 1UV. This is the first binuclear lanthanide complex that exhibits synergistic photocontrollable magnetic dynamics and photoluminescence. Ab initio calculations are conducted to understand the magnetostructural relationships of compounds 1, 1UV, and 2.

Synergy of Magnetic Anisotropy and Ferromagnetic Interaction Triggering a Dimeric Cr(II) Zero-Field Single-Molecule Magnet.

A novel CrII-dimeric complex, [CrIIN(SiiPr3)2(µ-Cl)(THF)]2 (1), has been successfully constructed using a bulky silyl-amide ligand. Single-crystal structure analysis reveals that complex 1 exhibits a binuclear motif, with a Cr2Cl2 rhombus core, where two equivalent tetra-coordinate CrII centers in the centrosymmetric unit display quasi-square planar geometry. The crystal structure has been well simulated and explored by density functional theory calculations. The axial zero-field splitting parameter (D < 0) with a small rhombic (E) value is unambiguously determined by systematic investigations of magnetic measurements, high-frequency electron paramagnetic resonance spectroscopy, and ab initio calculations. Remarkably, ac magnetic susceptibility data unveil that 1 features slow dynamic magnetic relaxation typical of single-molecule magnet behavior with Ueff = 22 K in the absence of a dc field. This increases up to 35 K under a corresponding static field. Moreover, magnetic studies and theoretical calculations point out that a non-negligible ferromagnetic coupling (FMC) exists in the dimeric Cr-Cr units of 1. The coexistence of magnetic anisotropy and FMC contributes to the first case of CrII-based single-molecule magnets (SMMs) under zero dc field.

Understanding the Magnetic Relaxation Mechanism in Mixed-Valence Dilanthanide Complexes with Metal-Metal Bonding: A Theoretical Investigation.

Theoretical investigations on mixed-valence dilanthanide complexes (CpiPr5)2Ln2I3 (Ln = Tb, Dy, and Ho) indicate that the total spin of the 4f shell couples preferentially to the σ electron spin and then to the orbital angular momentum, improving the strength of spin-orbit coupling (SOC) for each magnetic center. On the other hand, the concentration of negative charges containing the delocalized σ electron in the axial direction leads to a large crystal-field (CF) splitting. Both strong SOC and large CF splitting lead to the largest energy barrier Ueff of such complexes up to now. In addition, our calculations show that the introduction of σ electron can better suppress the quantum tunneling of magnetization in the ground spin-orbit state, and the Ueff of (CpiPr5)2Ln2I3 is expected to originate from the contribution of both Ln ions under such strong Ln-σ exchange coupling.

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal-Organic Supramolecular Assemblies.

The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal-organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 µmol h-1 g-1 . A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non-coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high-performance photocatalysts.

Largely Enhancing the Blocking Energy Barrier and Temperature of a Linear Cobalt(II) Complex through the Structural Distortion: A Theoretical Exploration.

Complete-active-space self-consistent field and N-electron valence second-order perturbation theory have both been employed to investigate the magnetic anisotropy of one two-coordinate cobalt(II) compound via altering the Co-C bond lengths and twist angle φ. The calculated energy barrier Ueff decreases with the decrease in the Co-C bond lengths due to the gradually increasing interaction between the 3d orbitals of CoII and the coordination ligand field and then to the decrease in the ground orbital angular moment L of CoII. Thus, we cannot improve Ueff simply by shortening the Co-C bond lengths. However, by rotating the twist angle φ from 60 to 0°, it is surprising to find that the energy barrier and blocking temperature can be enhanced up to 1559.1 cm-1 and 90 K, respectively, with φ = 0°, which are prominent even among lanthanide-based single-molecule magnets.

Five-Coordinated Dysprosium Single-Molecule Magnet Functionalized by the SMe Group.

A five-coordinate mononuclear Dy(III) complex with a C4v geometry (square-pyramid), [Dy(X)(DBP)2(TMG(H))2] [X = 3-(methylthio)-1-propoxide, DBP = 2,6-di-tert-butylphenoxide, and TMG(H) = 1,1,3,3-tetramethylguanidine] (1), was designed and synthesized. The complex displays a large anisotropy barrier of 432 cm-1 in the absence of a dc magnetic field benefiting from the strong interaction between the phenolate and Dy(III) ion. Ab initio calculations reveal that the most possible relaxation pathway is going through the second excited state. The terminal SMe group in the apical position furnishes the possibility of depositing it on the Au surface by the strong Au-S bond.

Series of Benzoquinone-Bridged Dicobalt(II) Single-Molecule Magnets.

Mononuclear complexes within a particular coordination geometry have been well recognized for high-performance single-molecule magnets (SMMs), while the incorporation of such well-defined geometric ions into multinuclear complexes remains less explored. Using the rigid 2-(di(1H-pyrazol-1-yl)methyl)-6-(1H-pyrazol-1-yl)pyridine (PyPz3) ligand, here, we prepared a series of benzoquinone-bridged dicobalt(II) SMMs [{(PyPz3)Co}2(L)][PF6]2, (1, L = 2,5-dioxo-1,4-benzoquinone (dhbq2-); 2, L = chloranilate (CA2-); and 3, L = bromanilate (BA2-)), in which each Co(II) center adopts a distorted trigonal prismatic (TPR) geometry and the distortion increases with the sizes of 3,6-substituent groups (H (1) < Cl (2) < Br (3)). Accordingly, the magnetic study revealed that the axial anisotropy parameter (D) of the Co ions decreased from -78.5 to -56.5 cm-1 in 1-3, while the rhombic one (E) increased significantly. As a result, 1 exhibited slow relaxation of magnetization under a zero dc field, while both 2 and 3 showed only the field-induced SMM behaviors, likely due to the increased rhombic anisotropy that leads to the serious quantum tunneling of the magnetization. Our study demonstrated that the relaxation dynamics and performances of a multinuclear complex are strongly dependent on the coordination geometry of the local metal ions, which may be engineered by modifying the substituent groups.

Impact of Ligand Substituents on the Magnetization Dynamics of Mononuclear DyIII Single-Molecule Magnets.

Two mononuclear DyIII single-molecule magnets with different ligand substituents located far from the coordinating atoms, [Dy(L-NO2)(NO3)] (1) and [Dy(L-Me)(NO3)] (2), and their diamagnetic-ion diluted analogues, 1' and 2', were structurally and magnetically characterized. 1 and 2 have nearly identical coordination environments of DyIII ions with D2d symmetry but different magnetization dynamics. No Orbach process was observed for 1 and 1' in the testing temperature and frequency range, but effective energy barriers of 575 and 829 K for 2 and 2' were obtained, respectively. The opened hysteresis loops were observed until 6 K for 1 and 10 K for 2. Ab initio calculations reveal that the energy gaps between ground and low-lying excited states of 2 are higher than those of 1 and the relaxation rate through quantum tunneling of magnetization of 2 is lower than that of 1 due to the electronic effect of the axial coordinating oxygen atoms influenced by ligand substitutions.

Magnetooptical Properties of Lanthanide(III) Metal-Organic Frameworks Based on an Iridium(III) Metalloligand.

Integrating magnetic and optical properties into a metal-organic framework (MOF) remains a great challenge. Herein, we have reasonably constructed two 3D magnetooptical MOFs by incorporating a [IrIII(ppy)2(bpy)]+-based fluorescent metalloligand and magnetic LnIII centers. The alternating arrangements of Δ- or Λ-[IrIII(ppy)2(bpy)]+ endow these MOFs with enhanced optical properties. Moreover, the use of DyIII leads to field-induced slow magnetic relaxation. This work provides an effective strategy for the preparation of magnetooptical bifunctional MOFs.

Hydrogen-Bonded Framework of a Cobalt(II) Complex Showing Superior Stability and Field-Induced Slow Magnetic Relaxation.

A unique hydrogen-bonded organic-inorganic framework (HOIF) constructed from a mononuclear cobalt(II) complex, [Co(MCA)2·(H2O)2] (HMCA = 4-imidazolecarboxylic acid), via multiple hydrogen-bonding interactions was synthesized and structurally characterized. The Co(II) center in the HOIF features a highly distorted octahedral coordination environment. Remarkably, the CoII HOIF showed permanent porosity with superior stability as established by combined thermogravimetric analysis (TGA), variable-temperature infrared spectra (IR), variable-temperature powder X-ray diffraction data (PXRD), and a CO2 isotherm. Structural studies reveal that short multiple hydrogen bonds should be responsible for the superior thermal and chemical stability of a HIOF. Magnetic investigations reveal the large easy-plane magnetic anisotropy of the Co2+ ions with the fitted D values being 22.1 (magnetic susceptibility and magnetization data) and 29.1 cm-1 (reduced magnetization data). In addition, the HOIF exhibits field-induced slow magnetic relaxation at low temperature with an effective energy barrier of Ueff = 45.2 cm-1, indicative of a hydrogen-bonded framework single-ion magnet of the compound. The origin of the significant magnetic anisotropy of the complex was also understood from computational studies. In addition, BS-DFT calculations indicate that the superexchange interactions between the neighboring CoII ions are non-negligible antiferromagnetism with JCo-Co = -0.5 cm-1. The foregoing results provide not only a carboxylate-imidazole ligand approach toward a stable HOIF but also a promising way to build a robust single-ion magnet via hydrogen-bond interactions.

Solvent Modification of the Structures and Magnetic Properties of a Series of Dysprosium(III) Single-Molecule Magnets.

Solvent effects on the structures and magnetic properties of single-molecule magnets (SMMs) have been of great interest for modification of the SMMs using chemical modulation. By systematically varying the reaction solvents (MeOH, ethanol, n-propanol, and n-butanol), we have successfully synthesized a series of DyIII-H4daps complexes (H4daps = N',N‴-[(1E,1'E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)]bis(2-hydroxybenzohydrazide), including two binuclear compounds, [Dy2(H2daps)2(MeOH)4(H2O)2](CF3SO3)2·0.5MeOH (1MeOH) and [Dy2(H2daps)3(EtOH)2]·2EtOH·Et2O (2EtOH), and two mononuclear compounds, [Dy(H4daps)2](CF3SO3)3·n-PrOH (3PrOH) and [Dy(H4daps)(CF3SO3)3(n-BuOH)]·0.5Et2O (4BuOH). Using different solvents, the ligand-to-metal ratios can be adjusted from 1:1 in 1MeOH and 4BuOH to 3:2 in 2EtOH and 2:1 in 3PrOH. Through the solvent crossover experiments, the role of the solvents and the conditions to form these complexes were carefully studied. The size of the different alcohols, their coordination ability to the DyIII center, and the solubility of the complexes in these alcohols might affect the assembly process and lead to modification of the structures and magnetic properties of these DyIII-H4daps complexes. Magnetic studies revealed that these four complexes all exhibit slow magnetic relaxation under a zero or an applied direct-current field, with an energy barrier of about 100 K for the binuclear compound 1MeOH. In combination with theoretical calculations, the magnetic-structure relationship of these four compounds has been analyzed. This work demonstrates the crucial role of different solvent molecules in the fine-tuning of the structures and magnetic performances of different lanthanide complexes.

Side-Group Effect on the Slow Relaxations of {Dy2} Single-Molecule Magnets with Confined N2O6 Donors.

Deep insights into and substantial enhancement of the effective anisotropy energy barrier for magnetization reversal (Ueff) are vitally important for the technological applications of dysprosium(III)-based single-molecule magnets (Dy-SMMs). To fully refine the ligand-field effect on spin relaxation, four centrosymmetric {Dy2} entities with formula [Dy2(CH3OH)2L2(RCOO)2] (H2L = 2-hydroxy-N'-((pyridin-2-yl)methylene)benzohydrazide) have been solvothermally prepared by varying the side groups of carboxylate coligands (RCOO-, R = CF3 for 1, H for 2, CH3 for 3, and Cp2Fe for 4). Structural analyses reveal that all of the DyIII carriers in 1-4 have the same N2O6 donor environments, and the non-coordinative R groups attached to the equatorial carboxylate bridges have not substantially changed the binding ability of the shortest Dy-Ophenolate bonds located at the axial position of the ligand field. Interestingly, the side groups have monotonically decreased the zero-field Ueff barriers of these weak antiferromagnetically coupled {Dy2} analogues from 721 K down to 379 K. Further electronic structure calculations demonstrate that the main magnetic axes of 1-4 are highly dominated by these comparable Dy-Ophenolate short bonds, and the g tensors have produced gradually increased transverse components responsible significantly for the decreased Ueff barriers. Additionally, thermally assisted relaxations occur preferably through the second (for 1) and the first (for 2-4) Kramer doublets. These interesting findings afford a new side-group effect to comprehensively understand the magnetostructural relationships and advance the rational design of high-performance Dy-SMMs.