Influence of O-H⋠⋠⋠Pt interactions on photoluminescent response in the (Et4N)2{[Pt(bph)(CN)2][phenylene-1,4-diresorcinol]} framework.

Tunable photoluminescence (PL) is one of the hot topics in current materials science, and research performed on the molecular phases is at the forefront of this field. We present the new (Et4N)2[PtII(bph)(CN)2]⋅rez3⋅1/3H2O (Pt2rez3) (bph=biphenyl-2,2'-diyl; rez3=3,3",5,5"-tetrahydroxy-1,1':4',1"-terphenyl, phenylene-1,4-diresorcinol coformer, a linear quaternary hydrogen bond donor) co-crystal salt based on the recently appointed promising [PtII(bph)(CN)2]2- luminophore. Within the extended hydrogen-bonded subnetwork [PtII(bph)(CN)2]2- complexes and rez3 coformer molecules form two types of contacts: the rez3O-H⋅⋅⋅Ncomplex ones in the equatorial plane of the complex and non-typical rez3O-H⋅⋅⋅Pt ones along its axial direction. The combined structural, PL, and DFT approach identified the rez3O-H⋅⋅⋅Pt synthons to be crucial in promoting the noticeable uniform redshift of bph ligand centered (LC) emission compared to the LC emission of the (Et4N)2[PtII(bph)(CN)2]⋅H2O (Pt2) precursor, owing to the direct interference of the phenol group with the PtII-bph orbital system via altering the CT processes within. The high-resolution emission spectra for Pt2 and Pt2rez3 were successfully reproduced at 77 K by using the Franck-Cordon expressions. The possibility to tune PL properties along the plausible continuum of rez3O-H⋅⋅⋅Pt synthons is indicated, considering various scenarios of molecular occupation of the space above and below the complex plane.

Optical Phenomena in Molecule-Based Magnetic Materials.

Since the last century, we have witnessed the development of molecular magnetism which deals with magnetic materials based on molecular species, i.e., organic radicals and metal complexes. Among them, the broadest attention was devoted to molecule-based ferro-/ferrimagnets, spin transition materials, including those exploring electron transfer, molecular nanomagnets, such as single-molecule magnets (SMMs), molecular qubits, and stimuli-responsive magnetic materials. Their physical properties open the application horizons in sensors, data storage, spintronics, and quantum computation. It was found that various optical phenomena, such as thermochromism, photoswitching of magnetic and optical characteristics, luminescence, nonlinear optical and chiroptical effects, as well as optical responsivity to external stimuli, can be implemented into molecule-based magnetic materials. Moreover, the fruitful interactions of these optical effects with magnetism in molecule-based materials can provide new physical cross-effects and multifunctionality, enriching the applications in optical, electronic, and magnetic devices. This Review aims to show the scope of optical phenomena generated in molecule-based magnetic materials, including the recent advances in such areas as high-temperature photomagnetism, optical thermometry utilizing SMMs, optical addressability of molecular qubits, magneto-chiral dichroism, and opto-magneto-electric multifunctionality. These findings are discussed in the context of the types of optical phenomena accessible for various classes of molecule-based magnetic materials.

Tuning Crystal Packing and Magnetic Properties in a Series of [Dy12] Metallocubanes Based on Azobenzene Derivatives of Salicylic Acid.

A series of four new Dy12 dodecanuclear clusters based on azobenzene derivative ligands of salicylic acid (L1-L4) has been synthesized and characterized in the crystalline phase using X-ray diffraction on single crystal and powder, IR spectroscopy, elemental analysis, and DSC-TGA methods. It was revealed that all obtained clusters exhibit the formation of the similar metallic cluster nodes, as vertex-sharing heterocubanes, obtained from four Dy3+ cations, three bridging hydroxyl groups, and O atoms from the salicylic ligands. The coordination geometry around the Dy(III) centers has been carefully analyzed. Whereas Dy12-L1 and Dy12-L2 with L1 and L2 containing Me and OMe groups in para positions of the phenyl rings, respectively, form similar porous 3D diamond-like molecular networks due to CH-π interactions, for Dy12-L3 with L3 bearing NO2-electron-withdrawing group, the generation of 2D molecular grids assembled by π-π staking is observed, and for Dy12-L4 with L4 bearing phenyl substituent, 3D hexagonal channels have been generated. The complexes Dy12-L1, Dy12-L2, and Dy12-L3 exhibit a zero-field slow magnetic relaxation effect. After UV irradiation of Dy12-L1, a decrease of the magnetic anisotropy energy barrier displaying the possibility of control over magnetic properties by the external stimulus has been observed.

Desolvation-Induced Highly Symmetrical Terbium(III) Single-Molecule Magnet Exhibiting Luminescent Self-Monitoring of Temperature.

A conjunction of Single-Molecule Magnet (SMM) behavior and luminescence thermometry is an emerging research line aiming at contactless read-out of temperature in future SMM-based devices. The shared working range between slow magnetic relaxation and the thermometric response is typically narrow or absent. We report TbIII -based emissive SMMs formed in a cyanido-bridged framework whose properties are governed by the reversible structural transformation from [TbIII (H2 O)2 ][CoIII (CN)6 ] ⋅ 2.7H2 O (1) to its dehydrated phase, TbIII [CoIII (CN)6 ] (2). The 8-coordinated complexes in 1 show the moderate SMM effect but it is enhanced for trigonal-prismatic TbIII complexes in 2, showing the SMM features up to 42 K. They are governed by the combination of QTM, Raman, and Orbach relaxation with the energy barrier of 594(18) cm-1 (854(26) K), one of the highest among the TbIII -based molecular nanomagnets. Both systems exhibit emission related to the f-f electronic transitions, with the temperature variations resulting in the optical thermometry below 100 K. The dehydration leads to a wide temperature overlap between the SMM behavior and thermometry, from 6 K to 42 K. These functionalities are further enriched after the magnetic dilution. The role of post-synthetic formation of high-symmetry TbIII complexes in achieving the SMM effect and hot-bands-based optical thermometry is discussed.

Covalent Modification by Click Mechanochemistry: Systematic Installation of Pendant OH Groups in a MOF for Rigidity Control and Luminescence-Based Water Detection.

Covalent linker transformations in metal-organic frameworks (MOFs) enable their functionalization but often suffer from low conversions or require harsh conditions, including heating, corrosive reactants and solvents, or catalysts. In this work, using solvent-free mechanochemistry for the first time for such conversions, we demonstrate the systematic MOF pore modification with pendant hydroxyl groups and the resulting effects on the network rigidity, its luminescent properties, as well as adsorption of CO2 and vapors of methanol, ethanol, isopropanol, D2O, and H2O. A new zinc-based heterolinker MOF (JUK-20) containing both protic luminescent units and reactive tetrazine cores was used as a model and subjected to an inverse electron-demand Diels-Alder (iEDDA) click reaction with a series of dienophiles (x) of different lengths having OH groups. From the obtained series of JUK-20(Zn)-x MOFs, a flexible material capable of luminescent humidity sensing was identified, and the influence of water on the luminescence of the material was explained by analogy with the excited-state intramolecular proton transfer (ESIPT) model. In general, our results provide guidance for designing and tuning MOFs for luminescence-based detection using a stepwise synthetic approach.

Quantum Chaos and Level Dynamics.

We review the application of level dynamics to spectra of quantally chaotic systems. We show that the statistical mechanics approach gives us predictions about level statistics intermediate between integrable and chaotic dynamics. Then we discuss in detail different statistical measures involving level dynamics, such as level avoided-crossing distributions, level slope distributions, or level curvature distributions. We show both the aspects of universality in these distributions and their limitations. We concentrate in some detail on measures imported from the quantum information approach such as the fidelity susceptibility, and more generally, geometric tensor matrix elements. The possible open problems are suggested.

Applicability of shear wave elastography for lacrimal gland evaluation in primary Sjögren syndrome.

INTRODUCTION: Primary Sjögren syndrome (pSS) is a systemic autoimmune disease that mainly affects the salivary and lacrimal glands, leading to their progressive destruction. OBJECTIVES: The primary aim of this study was to verify whether shear wave elastography (SWE) of the lacrimal glands can be used to differentiate patients with pSS from healthy controls. The secondary aim was to assess whether there are any associations between SWE values, results of other ocular tests included in pSS diagnosis (the Schirmer test, ocular staining score [OSS]), and subjective symptoms of eye dryness. PATIENTS AND METHODS: The study included 45 patients with pSS (41 women, 4 men) and 108 healthy controls (104 women, 4 men). All pSS patients met the 2016 American College of Rheumatology / European League Against Rheumatism pSS classification criteria. The participants underwent bilateral SWE of the lacrimal glands with the results expressed in kilopascals (kPa). The Schirmer test was performed in all patients, and OSS was calculated only in the pSS group. RESULTS: The patients with pSS had significantly higher SWE values for the lacrimal glands than the controls. No significant differences in SWE results were observed between the groups of pSS patients with or without eye dryness confirmed by the Schirmer test and OSS, or the pSS patients with or without subjective symptoms of eye dryness. The optimal cutoff point for the diagnosis of pSS for the mean result of left and right lacrimal gland elastography was 7.2 kPa (sensitivity, 88.9%; specificity, 88%). Lacrimal gland SWE values may be a good classifier for the diagnosis of pSS, with an area under the receiver operating characteristic curve of 89.8 (95% CI, 81.5-98.1). CONCLUSIONS: SWE of the lacrimal glands is a noninvasive, quantitative method that seems to be a reliable additional examination tool to support the diagnosis of pSS. Its role among the functional tests has not yet been well defined. To confirm the usefulness of SWE for pSS diagnosis, a standardized and widely accepted study protocol should be defined first.

Elastography as a possible useful method of assessment of skin involvement in systemic sclerosis.

Introduction: Scleroderma (Sc) is a connective tissue disorder associated with internal organ involvement, increased mortality, and unknown pathogenesis. It has been found that the more extensive the skin involvement the more severe internal organ manifestations and increased disability. The Rodnan skin score (RSS) is one of the established methods to examine skin thickness among patients with Sc. Due to RSS limitations, for instance, lack of detection of subclinical changes, a new tool is needed for the evaluation of Sc. In recent studies, shear wave elastography (SWE) has been examined as a potential tool to assess skin involvement through the evaluation of skin strain. Aim: To verify whether elastography is a reliable method to examine Sc progression and possibly provide one useful site to perform the examination - as an easy, cheap, and reliable examination tool. Material and methods: Forty Sc patients were examined, and 28 healthy individuals were recruited for the control group. Among the patients and control group, skin thickness was assessed using the RSS and skin strain measurements using elastography in 20 body locations. Results: SWE in the right-hand finger can be treated as an important diagnostic indicator of the severity of Sc. Conclusions: SWE is a reliable method for evaluating skin involvement among patients with systemic sclerosis (SSc). Right finger measurements correlate positively with Rodnan's results and can be a predictor of the severity of SSc. This study found SWE to be a reliable method for examining SSc progression and possibly one useful site for the examination.

Supramolecular cis-"Bis(Chelation)" of [M(CN)6]3- (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG).

Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Shear wave elastography as a potential additional diagnostic tool in primary Sjögren's syndrome: an observational study.

The primary aim of this study was to verify if shear wave elastography can be used to evaluate salivary gland involvement in primary Sjögren's syndrome (pSS). The secondary objective was to establish an accurate cut-off value for parotid and submandibular salivary gland stiffness and to verify whether there are any distinctions among pSS patients with or without subjective mouth dryness. This prospective study included 45 patients with pSS (2016 ACR/EULAR classification criteria) and 108 healthy controls. All subjects underwent bilateral shear wave elastography of the parotid and submandibular salivary glands. Clinical data of pSS patients were collected and compared to elastography results. Patients with pSS had significantly higher shear wave elastography values for the parotid and submandibular salivary glands than the controls. There were no statistical differences in SWE values between patients with or without mouth dryness. The optimal cut-off value (mean value of 4 salivary glands shear wave elastography results) to distinguish patients with or without pSS was 13.19 kPa with sensitivity = 97.8% and specificity = 100.0%. It was, therefore, confirmed that shear wave elastography measurement of salivary glands has strong predictive ability in pSS detection (AUC 97.8%, 95% CI 93.4-100.0%). Shear wave elastography seems to be a promising, non-invasive and simple quantitative adjunct test to support the diagnosis of pSS with good sensitivity and specificity. More extensive prospective studies are needed to standardize a study protocol.

Phase Diagram of 1+1D Abelian-Higgs Model and Its Critical Point.

We determine the phase diagram of the Abelian-Higgs model in one spatial dimension and time (1+1D) on a lattice. We identify a line of first order phase transitions separating the Higgs region from the confined one. This line terminates in a quantum critical point above which the two regions are connected by a smooth crossover. We analyze the critical point and find compelling evidence for its description as the product of two noninteracting systems: a massless free fermion and a massless free boson. However, we find also some surprising results that cannot be explained by our simple picture, suggesting this newly discovered critical point is an unusual one.

Cold atoms meet lattice gauge theory.

The central idea of this review is to consider quantum field theory models relevant for particle physics and replace the fermionic matter in these models by a bosonic one. This is mostly motivated by the fact that bosons are more 'accessible' and easier to manipulate for experimentalists, but this 'substitution' also leads to new physics and novel phenomena. It allows us to gain new information about among other things confinement and the dynamics of the deconfinement transition. We will thus consider bosons in dynamical lattices corresponding to the bosonic Schwinger or [Formula: see text] Bose-Hubbard models. Another central idea of this review concerns atomic simulators of paradigmatic models of particle physics theory such as the Creutz-Hubbard ladder, or Gross-Neveu-Wilson and Wilson-Hubbard models. This article is not a general review of the rapidly growing field-it reviews activities related to quantum simulations for lattice field theories performed by the Quantum Optics Theory group at ICFO and their collaborators from 19 institutions all over the world. Finally, we will briefly describe our efforts to design experimentally friendly simulators of these and other models relevant for particle physics. This article is part of the theme issue 'Quantum technologies in particle physics'.

Tunable magnetic anisotropy in luminescent cyanido-bridged {Dy2Pt3} molecules incorporating heteroligand PtIV linkers.

The interest in the generation of photoluminescence in lanthanide(III) single-molecule magnets (SMMs) is driven by valuable magneto-optical correlations as well as perspectives toward magnetic switching of emission and opto-magnetic devices linking SMMs with optical thermometry. In the pursuit of enhanced magnetic anisotropy and optical features, the key role is played by suitable ligands attached to the 4f metal ion. In this context, cyanido complexes of d-block metal ions, serving as expanded metalloligands, are promising. We report two novel discrete coordination systems serving as emissive SMMs, {[DyIII(H2O)3(tmpo)3]2[PtIVBr2(CN)4]3}·2H2O (1) and {[DyIII(H2O)(tmpo)4]2[PtIVBr2(CN)4]3}·2CH3CN (2) (tmpo = trimethylphosphine oxide), obtained by combining DyIII complexes with uncommon dibromotetracyanidoplatinate(IV) ions, [PtIVBr2(CN)4]2-. They are built of analogous Z-shaped cyanido-bridged {Dy2Pt3} molecules but differ in the coordination number of DyIII (C.N. = 8 in 1, C.N. = 7 in 2) and the number of coordinated tmpo ligands (three in 1, four in 2) which is related to the applied solvents. As a result, both compounds reveal DyIII-centred slow magnetic relaxation but only 1 shows SMM character at zero dc field, while 2 is a field-induced SMM. The relaxation dynamics in both systems is governed by the Raman relaxation mechanism. These effects were analysed using ac magnetic data and the results of the ab initio calculations with the support of magneto-optical correlations based on low-temperature high-resolution emission spectra. Our findings indicate that heteroligand halogeno-cyanido PtIV complexes are promising precursors for emissive SMMs with the further potential of sensitivity to external stimuli that may be related to the lability of the axially positioned halogeno ligands.

Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of YbIII Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals.

The ab initio calculations were correlated with magnetic and emission characteristics to understand the modulation of properties of NIR-emissive [YbIII(2,2'-bipyridine-1,1'-dioxide)4]3+ single-molecule magnets by cyanido/thiocyanidometallate counterions, [AgI(CN)2]- (1), [AuI(SCN)2]- (2), [CdII(CN)4]2-/[CdII2(CN)7]3- (3), and [MIII(CN)6]3- [MIII = Co (4), Ir (5), Fe (6), Cr (7)]. Theoretical studies indicate easy-axis-type ground doublets for all YbIII centers. They differ in the magnetic axiality; however, transversal g-tensor components are always large enough to explain the lack of zero-dc-field relaxation. The excited doublets lie more than 120 cm-1 above the ground one for all YbIII centers. It was confirmed by high-resolution emission spectra reproduced from the ab initio calculations that give reliable insight into energies and oscillator strengths of optical transitions. These findings indicate the dominance of Raman relaxation with the power n varying from 2.93(4) to 6.9(2) in the 4-3-5-1-2 series. This trend partially follows the magnetic axiality, being deeper correlated with the phonon modes schemes of (thio)cyanido matrices.

Constraint-Induced Delocalization.

We study the impact of quenched disorder on the dynamics of locally constrained quantum spin chains, that describe 1D arrays of Rydberg atoms in both the frozen (Ising-type) and dressed (XY-type) regime. Performing large-scale numerical experiments, we observe no trace of many-body localization even at large disorder. Analyzing the role of quenched disorder terms in constrained systems we show that they act in two, distinct and competing ways: as an on-site disorder term for the basic excitations of the system, and as an interaction between excitations. The two contributions are of the same order, and as they compete (one towards localization, the other against it), one does never enter a truly strong disorder, weak interaction limit, where many-body localization occurs. Such a mechanism is further clarified in the case of XY-type constrained models: there, a term which would represent a bona fide local quenched disorder term acting on the excitations of the clean model must be written as a series of nonlocal terms in the unconstrained variables. Our observations provide a simple picture to interpret the role of quenched disorder that could be immediately extended to other constrained models or quenched gauge theories.

Three-electron correlations in strong laser field ionization.

Strong field processes involving several active electrons reveal unambiguous dynamical signatures of the Pauli principle importance even in the nonrelativistic regime. We exemplify this statement studying three active electrons model atoms interacting with strong pulsed radiation, using an ab-initio time-dependent Schrödinger equation on a grid. In our restricted dimensionality model we are able to analyze momenta correlations of the three outgoing electrons using Dalitz plots. The different symmetries of the electronic wavefunctions, directly related to the initial state spin components, appear clearly visible.

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets.

Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4- ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f-f electronic transitions. Moreover, they reveal DyIII-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu4N][YIII0.9DyIII0.1(BH4)4] (1@Y) and [Ph4P][YIII0.9DyIII0.1(BH4)4] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1-2 and the highly symmetrical inorganic DyIII borohydrides, α/ß-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior.

Solvent- and Temperature-Driven Photoluminescence Modulation in Porous Hofmann-Type SrII-ReV Metal-Organic Frameworks.

A unique family of three-dimensional (3D) luminescent SrII-ReV metal-organic frameworks (MOFs), {[SrII(MeOH)5][ReV(CN)4(N)(bpen)0.5]·MeOH}n [1·MeOH; N3- = nitrido ligand, bpen = 1,2-bis(4-pyridyl)ethane, and MeOH = methanol], {[SrII(MeOH)4][ReV(CN)4(N)(bpee)0.5]·2MeOH}n [2·MeOH; bpee = 1,2-bis(4-pyridyl)ethylene], and {[SrII(bpy)0.5(MeOH)2][ReV(CN)4(N)(bpy)0.5]}n (3·MeOH; bpy = 4,4'-bipyridine), is reported. They are obtained by the molecular self-assembly of Sr2+ ions with tetracyanidonitridorhenate(V) metalloligands, [ReV(CN)4(N)]2-, and pyridine-based organic spacers (L = bpen, bpee, bpy). Such a combination of molecular precursors results in bimetallic SrII-ReV cyanido-bridged layers further bonded by organic ligands into pillared Hofmann-type coordination skeletons. Because of the formation of {ReV-(L)-ReV} moieties providing emissive metal-to-ligand charge-transfer states, 1·MeOH-3·MeOH exhibit solid-state room-temperature photoluminescence tunable from green to orange by the applied organic ligand. The most stable MOF of 3·MeOH, based on the alternating {ReV-(bpy)-ReV} and {SrII-(bpy)-SrII} linkages, exhibits three interconvertible, variously solvated phases, methanol-solvated 3·MeOH, hydrated {[SrII(bpy)0.5(H2O)2][ReV(CN)4(N)(bpy)0.5]·0.6H2O}n (3·H2O), and desolvated {[SrII(bpy)0.5][ReV(CN)4(N)(bpy)0.5]}n (3). Their formation was correlated with water and methanol vapor sorption properties investigated for 3·H2O. The solvent content affects the luminescence mainly by tuning the emission energy within the series of 3·MeOH, 3·H2O, and 3. All of the obtained compounds exhibit temperature-driven modulation of luminescence, including the shift of the emission maximum and lifetime. The thermochromic luminescent response was found to be sensitive to the presence and type of solvent in the crystal lattice. This work shows that the construction of [ReV(CN)4(N)]2--based MOFs is an efficient route toward advanced solid luminophores tunable by external stimuli such as solvent or temperature.

A systematic construction of Gaussian basis sets for the description of laser field ionization and high-harmonic generation.

A precise understanding of mechanisms governing the dynamics of electrons in atoms and molecules subjected to intense laser fields has a key importance for the description of attosecond processes such as the high-harmonic generation and ionization. From the theoretical point of view, this is still a challenging task, as new approaches to solve the time-dependent Schrödinger equation with both good accuracy and efficiency are still emerging. Until recently, the purely numerical methods of real-time propagation of the wavefunction using finite grids have been frequently and successfully used to capture the electron dynamics in small one- or two-electron systems. However, as the main focus of attoscience shifts toward many-electron systems, such techniques are no longer effective and need to be replaced by more approximate but computationally efficient ones. In this paper, we explore the increasingly popular method of expanding the wavefunction of the examined system into a linear combination of atomic orbitals and present a novel systematic scheme for constructing an optimal Gaussian basis set suitable for the description of excited and continuum atomic or molecular states. We analyze the performance of the proposed basis sets by carrying out a series of time-dependent configuration interaction calculations for the hydrogen atom in fields of intensity varying from 5 × 1013 W/cm2 to 5 × 1014 W/cm2. We also compare the results with the data obtained using Gaussian basis sets proposed previously by other authors.

Reversible Humidity-Driven Transformation of a Bimetallic {EuCo} Molecular Material: Structural, Sorption, and Photoluminescence Studies.

Functional molecule-based solids built of metal complexes can reveal a great impact of external stimuli upon their optical, magnetic, electric, and mechanical properties. We report a novel molecular material, {[EuIII(H2O)3(pyrone)4][CoIII(CN)6]}·nH2O (1, n = 2; 2, n = 1), which was obtained by the self-assembly of Eu3+ and [Co(CN)6]3- ions in the presence of a small 2-pyrrolidinone (pyrone) ligand in an aqueous medium. The as-synthesized material, 1, consists of dinuclear cyanido-bridged {EuCo} molecules accompanied by two H-bonded water molecules. By lowering the relative humidity (RH) below 30% at room temperature, 1 undergoes a single-crystal-to-single-crystal transformation related to the partial removal of crystallization water molecules which results in the new crystalline phase, 2. Both 1 and 2 solvates exhibit pronounced EuIII-centered visible photoluminescence. However, they differ in the energy splitting of the main emission band of a 5D0 → 7F2 origin, and the emission lifetime, which is longer in the partially dehydrated 2. As the 1 ↔ 2 structural transformation can be repeatedly reversed by changing the RH value, the reported material shows a room-temperature switching of detailed luminescent features including the ratio between emission components and the emission lifetime values.