dataesr/scientific-paragraphs-categorization huggingface dataset:
In particular, the former (110)/(104) edge have been recently considered as a privileged site for strong TiCl 4 adsorption to generate a stereo-selective active site  10, 17  bringing tetracoordinated sites (T) close to pentacoordinated (P) ones; also in our models of MgCl 2 support the T sites with attached TiCl 4 molecules lie close to P sites. Relative stabilities of nanoplates is evaluated by considering the cluster formation reaction starting from bulk MgCl 2 and gas phase TiCl 4 ; the relative energy, E cluster , has been computed from the calculated energy of a structure (E) according to the formula E cluster = E -N MgCl 2 • E MgCl 2 -M TiCl 4 • E TiCl 4 ( 1 ) where  All data are collected in Table  2  including (only for binary CO/MgCl 2 systems) results from regular surfaces exposing Mg atoms with the same coordination number (from periodic 2D calculations).
ACKNOWLEDGEMENTS Access to the HPC resources of CINECA has been appreciated. ISIS  Rutherford Appleton Laboratory UKRI, NScD Oak Ridge National Laboratory , European Spallation for experiments and  SCARF Scientific Computing Department ,  STFC Rutherford Appleton Laboratory  for computer facilities. Dr. Svemir Rudic  and  Jonatan Roddom  are kindly acknowledged for technical support. Access to the HPC resources of CINES/IDRIS/TGCC obtained thanks to the grant  2020-[A0080810471 ] made by  GENCI  is also warmly acknowledged. The work of  Gentoku Takasao  was supported by  JSPS KAKENHI  Grant Number  JP20J15042. corresponding authors*: maddalena. damore@unito. it,taniike@jaist. ac. jp.
Coupling constants (J) are given in Hz, multiplicities are named as singlet (s), doublet (d), triplet (t), quartet (q), multiplet or overlapping signals (m) and broad signal (br), solvent is given in parenthesis. GC-MS spectra were collected on a Shimadzu GCMS-QP2010 Ultra gas chromatograph mass spectrometer equipped with a Supelco SLB TM -MS fused silica capillary (30 m x 0. 25 mm x 0. 25 μm). Elemental analyses of samples sealed under vacuum were performed under inert atmosphere by Medac Ltd at Chobham (Surrey, UK) or Analytische laboratorien at Lindlar (Germany). Crystallography. The data were collected at 100(2) K on a Nonius Kappa-CCD area detector diffractometer  25  using graphitemonochromated Mo Kα radiation (λ = 0. 71073 Å). The crystals were introduced into glass capillaries with a protective coating of Paratone-N oil (Hampton Research).
The data (combinations of and -scans with a minimum redundancy of at least 4 for 90% of the reflections) were processed with HKL2000. 25  Absorption effects were corrected empirically with SCALEPACK. 26  The structures were solved by intrinsic phasing with SHELXT,  27  expanded by subsequent difference Fourier synthesis and refined by full-matrix least-squares on F 2 with SHELXL. 28  All non-hydrogen atoms were refined with anisotropic displacement parameters. When present, the hydrogen atoms bound to iridium and nitrogen atoms were retrieved from residual electron density maps and were fully refined. The carbon-bound hydrogen atoms were introduced at calculated positions and were treated as riding atoms with an isotropic displacement parameter equal to 1. 2 times that of the parent atom (1.
57  The slightly longer bond lengths in 5 certainly reflect the higher coordination number. These Ir-C1 distances of 1. 990(3) Å and 2. 024(4) Å in 2 and 5, respectively, vary from 1. 961(6) Å to 2. 10(1) Å in a series of seventy-seven R POCOP iridium(I) and iridium(III) complexes reported in the Cambridge Structural Database (CSD, version 5. 40)  57  and in which the Ir-P distances extend over the range 2. 2408(9)-2. 412(1) Å. The Ir-η 1 -O(OTf) is classical for Ir-OTf complexes  58  and the Ir-N(acetonitrile) distances in 5 are comparable to those found in the two other reported iridium(III)acetonitrile pincer complexes. 59, 60  The Ir-H distances in 2 (1. 52(4) Å) and 5 (1. 46(4) Å) are quite identical to those in the complexes [( tBu POCOP)IrHCl] (1. 49(6) Å),  61  the cation [( tBu- POCOP)IrH(HSiEt3)][B(C6F5)4] (1.
Accession Codes CCDC 2077245-2077248  contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www. ccdc. cam. ac. uk/data_request/cif, or by emailing data_request@ccdc. cam. ac. uk, or by contacting The  Cambridge Crystallographic Data Centre , 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
The DLS autocorrelation functions were obtained at a scattering angle of 90 • and a temperature of 20 • C. The intensity-weighted relaxation time (τ) distributions were extracted from the autocorrelation data using the multi-exponential CONTIN method. The apparent diffusion coefficients (D app ) were obtained by considering D app = (1/τq 2 ) where τ is the mean relaxation time and q the scattering vector. The hydrodynamic radii (R H ) were determined using the Stokes-Einstein relation, R H = k B T 6πηD where k B is the Boltzmann constant, T the temperature, η the viscosity of the solvent, and D the diffusion coefficient. ζ potential measurements were performed with a Zetasizer Nano-ZS (Malvern Instruments, Malvern, UK) at an angle of 173 • using a 4. 0 mW He-Ne laser operating at a wavelength of 632.
8 nm. An automatic titrator MPT-2 (Malvern Instruments) was coupled to the Zetasizer allowing successive injections of one PE (titrant) into the second (titrated). The electrophoretic mobility of each solution was measured and converted to ζ potential (mV) by the Smoluchowski approximation model using the DTS program (Malvern). Small-angle X-ray scattering (SAXS). SAXS profiles were acquired on a XEUSS set-up (Xenocs, Grenoble, France) with a microfocus copper anode source, a scatterless collimation system, and a PILATUS 2-D detector, giving access to scattering wave vector q values from 0. 009 to 0. 5 Å -1. The PEC and individual PEs were put in thin glass capillaries. The resulting 2D images were found to be isotropic, and the data were azimuthally averaged to give the intensity scattering curve I(q), corrected for the experimental background, as a function of q = (4π/λ)sin θ, where λ = 0.
0001 g•m -3. l c was obtained by analyzing the static interfacial profile near the vertical wall of the cell with a shape given by the generalized Young-Laplace equation connecting capillary pressure with curvature and surface tension for the case of a flat wall as  [37, 38] : x l c = arccosh 2l c y -arccosh 2l c h + 4 - h 2 l 2 c 1/2 -4 - y 2 l 2 c 1/2 (2) where x is the distance to the vertical wall, y the height of the profile above the flat level far away from the wall, and h is the meniscus contact height at x = 0. The (X,Y) profile was observed and recorded using an optical microscope (X5 objective) rotated by 90 • equipped with a digital camera, computed using the ImageJ software and finally fitted to Equation  (2). The left and right profiles on both sides of the cell were measured and averaged.
The measurements were carried out while the sample was rotated about the vertical axis within 180 • with a step of 1 • (for the 72 and 600 mK datasets) or 3 • (other temperatures), with subsequent averaging of the datasets to compensate for the preferred orientations of individual crystallites. The data were collected at several temperatures between 72 and 600 mK in zero magnetic field, allowing for sufficient time for temperature stabilization before every data collection. The measurements at base temperature and at 600 mK were measured with higher statistics, corresponding to approximately 13 h acquisition time per temperature for the 72 and 600 mK datasets. The 600 mK dataset, collected above T N , is plotted in Fig. 2 (a). Apart from the structural reflections from the main KCeS 2 phase, it contains reflections from the paramagnetic impurity phase Ce 2 O 2 S  [58, 59] , which constitutes about 15% of our sample judging from the results of structural refinement but exhibits no magnetic Bragg reflections.
There are also two intense peaks from metallic copper that originate from the sample container, which we included as the third phase. Our Rietveld refinement of the neutron data was done in the assumption of the rhombohedral R3m space group, previously reported for KCeS 2 from x-ray structure refinement  [54, 60]. The agreement between the lattice structures obtained at room temperature and at 600 mK (apart from the changes in lattice constants due to thermal expansion) demonstrates the absence of any symmetry-lowering transitions down to T N. The low-temperature lattice parameters resulting from the refinement of our neutron data are summarized in Table  1. The magnetic peaks, shown in the 72 mK dataset in Fig. 2 (b ) with black arrows, set in below 400 mK -the transition temperature revealed earlier in specific-heat measurements  [54].
The difference of the low-and high-temperature datasets, plotted in Fig. 2  (c), contains only magnetic Bragg peaks, whereas the structural scattering from KCeS 2 and the oxysulphide impurity phase is subtracted to zero, which Table  1. Low-temperature unit cell parameters, χ 2 values, and R factors for our refinement of neutron diffraction data on the majority phase KCeS 2 and minority phase Ce 2 O 2 S at T = 72 and 600 mK. Here V is the unit cell volume, z(S) is the z position of S on the 6c Wyckoff site in KCeS 2 , and z(Ce) and z(O) are the positions of Ce and O on the 4h Wyckoff site in Ce 2 O 2 S, respectively. ) was determined by the K_Search algorithm in the FullProf Suite based on difference of the two datasets. Representation analysis carried out with SARAh  [61]  for the R3m space group with the aforementioned propagation vector suggests two possible common irreducible representations: Γ 2 and Γ 4 , which we have checked against the temperature-subtracted I(0.
072 K) -I(0. 6 K) dataset. Our final result of the magnetic structure refinement, which was done using FullProf Suite  [62] , is shown in Fig. 2 (c ) with a black line. The magnetic signal can be perfectly described only using the Γ 2 irreducible representation. Note that the two peaks marked with red arrows are of nonmagnetic origin, as they result from the imperfect subtraction of strong structural reflections from Cu. The magnetic structure of KCeS 2 is collinear, with spins lying approximately in the ab plane and pointing orthogonally to the nearest-neighbor Ce-Ce bonds, as shown in the inset to Fig. 2 (d ). The refinement suggests a statistically insignificant out-of-plane canting of Ce 3+ spins by (5. 5 ± 5) • , yet fixing this angle to zero has no significant effect on the quality of the fit, so also the in-plane spin arrangement would be consistent with our data.
1 Å from the experimental value. For example, for KCeS 2 (CeS 6 cluster) the energies for the second and third states can change almost twofold and threefold, respectively, in this range. At the same time for Ce 2 O 2 S the situation is much more complex. Apart from the pronounced energy change, the system undergoes two local phase transitions from the easy-axis to easy-plane and back to easy-axis as δ z changes from 0. 0 to 0. 1. The detailed analysis of this phenomenon is outside the scope of this work, so we leave it for follow-up studies. In the following, we compare relative state energies around the experimental geometries and their compositions (Table  2 ). In our previously published inelastic neutron scattering (INS) data  [54] , we observed one additional CEF excitation beyond those allowed for the Ce 3+ ion in KCeS 2.
Acknowledgments This project was funded in part by the  German Research Foundation (DFG)  under the individual research grant  IN 209/9-1 , via the project  C03  of the Collaborative Research Center  SFB 1143  (project-id 247310070) at the  TU Dresden , and the  Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter -ct. qmat ( EXC 2147 , project-id 390858490). S. A. thanks  A. Popov  ( IFW, Dresden ) and  M. Vojta  ( TU Dresden ) for fruitful discussions and acknowledges financial support from the  German Research Foundation (DFG)  under Grant No. AV 169/3-1. We also acknowledge  V. Joyet  and  S. Djellit  for technical assistance and  Institut Laue-Langevin, Grenoble (France)  for providing neutron beam time [78].
Materials and Physical Measurements All reagents and solvents for synthesis were commercially purchased and used without any further purification. The bis-semicarbazone ligand L was synthesized according to the method reported in the literature  [42]. IR spectra were recorded on a FTIR Bruker Tensor V-37 spectrophotometer (KBr pellets) in the range of 4000-400 cm -1. Elemental analysis was performed on a EuroEA Elemental Analyzer. Magnetic Studies: DC magnetic susceptibility data (2-300K) were collected on powdered samples using a SQUID magnetometer (Quantum Design MPMS-XL), applying a magnetic field of 0. 1 T. All data were corrected for the contribution of the sample holder and the diamagnetism of the samples estimated from Pascal's constants  [43, 44]. The field dependence of the magnetization (up to 5 T) was measured between 2.
0 and 5. 0 K. AC magnetic susceptibility was measured between 2 and 7 K with an oscillating field magnitude of Hac = 3. 0 Oe and frequency ranging between 1 and 1488 Hz in presence of a dc field up to Hdc = 4000 Oe. Fitting of the variable parameters and estimation of errors was performed with lsqcurvefit solver in MATLAB, and jacobian matrix was used to generate Scheme 1. The structure of bis-semicarbazone ligand, L. The new compounds have been characterized by single-crystal X-ray diffraction, and their magnetic properties have been investigated.
Materials and Physical Measurements All reagents and solvents for synthesis were commercially purchased and used without any further purification. The bis-semicarbazone ligand L was synthesized according to the method reported in the literature  [42]. IR spectra were recorded on a FTIR Bruker Tensor V-37 spectrophotometer (KBr pellets) in the range of 4000-400 cm -1. Elemental analysis was performed on a EuroEA Elemental Analyzer. Magnetic Studies: DC magnetic susceptibility data (2-300 K) were collected on powdered samples using a SQUID magnetometer (Quantum Design MPMS-XL), applying a magnetic field of 0. 1 T. All data were corrected for the contribution of the sample holder and the diamagnetism of the samples estimated from Pascal's constants  [43, 44]. The field dependence of the magnetization (up to 5 T) was measured between 2.
0 and 5. 0 K. AC magnetic susceptibility was measured between 2 and 7 K with an oscillating field magnitude of H ac = 3. 0 Oe and frequency ranging between 1 and 1488 Hz in presence of a dc field up to H dc = 4000 Oe. Fitting of the variable parameters and estimation of errors was performed with lsqcurvefit solver in MATLAB, and jacobian matrix was used to generate 95% confidence intervals on the fitted parameters. Typical examples of this analysis are presented in Figures  S3-S6. X-ray powder diffraction data were measured on a Proto AXRD benchtop using Cu-Kα radiation with a wavelength of 1. 54059 Å in the range of 5-35º (2θ).
Single Crystal X-ray Crystallography X-ray diffraction data were collected at 293 K on a Rigaku XtaLAB Synergy-S diffractometer operating with Mo-Kα (λ = 0. 71073 Å) micro-focus sealed X-ray tube. The structures were solved by direct methods and refined by full-matrix least squares techniques based on F 2. The non-H atoms were refined with anisotropic displacement parameters. Calculations were performed using SHELX-2014 or SHELX-2018 crystallographic software package  [45, 46]. Supplementary X-ray crystallographic data in CIF format have been deposited with the CCDC with the following reference numbers: 2069217 (1 GdFe ), 2069215 (2 DyFe ), and 2069216 (3 DyCo ). A summary of the crystallographic data and the structure refinement for crystals 1-3 are given in Table  S1.
Synthesis of Complexes The three compounds are synthesized following the same general procedure: LnCl 3 •6H 2 O (0. 06 mmol) and L (0. 06 mmol) in 10 mL H 2 O were stirred at 80 • C for 30 min. The abovecooled solution was filtered and transferred to a 30 mL test tube. Additional 5 mL of water was layered over the aqueous solution of the mononuclear complexes, and finally, a 10 mL H 2 O solution containing 0. 06 mmol K 3 [Fe(CN) 6 ] or K 3 [Co(CN) 6 ] was then slowly layered on top. The whole set up was kept undisturbed and slow diffusion of these two solutions led, after 2 weeks, to single crystals. The reaction mixture was mechanically stirred and was filtered off through frit followed by drying under vacuum to obtain a polycrystalline solid. Single crystals required for the X-ray data collections were picked up from the crystalline mixtures prior to mechanical stirring.
5 + x, 0. 5 -y, 1 -z), and two aqua ligands (O3, O4). The Ln-N bond lengths with the organic ligand are in the range of 2. 584(6) -2. 598(6) Å for 1GdFe and 2. 562(2) -2. 574(2) for 3DyCo, respectively, while for the cyanido groups are Gd1-N8 = 2. 534(6), Gd1-N13' = 2. 566  (6) , respectively, Dy1-N8 = 2. 519(3) and Dy1-N13' = 2. 544(3). The Ln-O bond lengths are slightly longer with the organic ligand than aqua ligands: Gd1-O1 = 2. 423(5), Gd1-O2 = 2. 406(5), Gd1-O3 = 2. 330(5), Gd1-O4 = 2. 375(5), Dy1-O1 = 2. 398(2), Dy1-O2 = 2. 382(2), Dy1-O3 = 2. 308(2), Dy1-O4 = 2. 3518(19) Å. The coordination geometry of the gadolinium ion can be described as spherical capped square antiprism, according to the calculations made with SHAPE software (Table  S2 )  [48]. The O3 aqua ligands are further connected by hydrogen bonding to neighboring chains generating a 2D supramolecular architecture in the crystallographic ac plane (Fig-  The lanthanide ions are nine-coordinated by the pentadentate organic ligand (O1, O2, N3, N4, and N5), two nitrogen atoms arising from the cyanido bridges (N8, N13 ; symmetry code: = -0.
5 + x, 0. 5y, 1z), and two aqua ligands (O3, O4). The Ln-N bond lengths with the organic ligand are in the range of 2. 584(6) -2. 598(6) Å for 1 GdFe and 2. 562(2) -2. 574(2) for 3 DyCo , respectively, while for the cyanido groups are Gd1-N8 = 2. 534(6), Gd1-N13 = 2. 566  (6) , respectively, Dy1-N8 = 2. 519(3) and Dy1-N13 = 2. 544(3). The Ln-O bond lengths are slightly longer with the organic ligand than aqua ligands: Gd1-O1 = 2. 423(5), Gd1-O2 = 2. 406(5), Gd1-O3 = 2. 330(5), Gd1-O4 = 2. 375(5), Dy1-O1 = 2. 398(2), Dy1-O2 = 2. 382(2), Dy1-O3 = 2. 308(2), Dy1-O4 = 2. 3518(19) Å. The coordination geometry of the gadolinium ion can be described as spherical capped square antiprism, according to the calculations made with SHAPE software (Table  S2 )  [48]. The O3 aqua ligands are further connected by hydrogen bonding to neighboring chains generating a 2D supramolecular architecture in the crystallographic ac plane (Figure  2  The extension of the supramolecular architecture to 3D is also mediated by hydrogen bond interactions involving the second aqua ligand, the crystallization water molecules and cyanido groups of the anionic metalloligand (Figure  3 ).
Conceptualization, D. D. and M. A. ; methodology, M. A. , D. D. and G. N. ; formal analysis, G. N. and A. M. M. ; investigation, D. D. , A. M. M. and G. N. ; writing-original draft preparation, D. D. and M. A. ; writing-review and editing, M. A. and G. N. All authors have read and agreed to the published version of the manuscript. " Funding: MAGMOLMET, grant ID: 867445 Acknowledgments: D. D. is grateful to the European Union's Horizon 2020 research and innovation programme, for financial support (MAGMOLMET, grant ID: 867445).
Author Contributions: Conceptualization, D. D. and M. A. ; methodology, M. A. , D. D. and G. N. ; formal analysis, G. N. and A. M. M. ; investigation, D. D. , A. M. M. and G. N. ; writing-original draft preparation, D. D. and M. A. ; writing-review and editing, M. A. and G. N. All authors have read and agreed to the published version of the manuscript. " Funding: MAGMOLMET, grant ID: 867445 Acknowledgments: D. D. is grateful to the European Union's Horizon 2020 research and innovation programme, for financial support (MAGMOLMET, grant ID: 867445).
Acknowledgements We thank the  AINSE Early Career Research Grant ,  Victoria University of Wellington, University Research Fund  (M. D. A),  AINSE   Honours Scholarship, Curtis-Gordon Research Scholarship ,  Dr. Margaret L. Bailey Award  and  Victoria University of Wellington Doctoral Scholarship (G. M. R)  for financial support for this work. L. M. is a senior member of the  Institut Universitaire de France. CalMip is acknowledged for a generous grant of computing time.
Acknowledgements This work was supported by  CEA  and  ANR  ( ANR-17-CE07-0035-01 ). The authors thank  T. d'Anfray ,  A. Goudet ,  S. Lebrequier  and  D. -A. Buisson  ( DRF-JOLIOT-SCBM, CEA ) for the excellent analytical support and  Dr. L. Plougastel  and  S. Gabillet  for preliminary experiments. Computations presented in this work were performed on the Kong cluster at  NJIT. We wish to thank as well  Prof K. N. Houk  ( University of California, Los Angeles ) for his mentorship over the course of this project.
Synthesis of the Coumarins All reagents and solvents were purchased from Aldrich, Alfa Aesar, or TCI Europe and used as received without further purification. Mass spectroscopy was performed by the Spectropole of Aix-Marseille University. ESI mass spectral analyses were recorded with a 3200 QTRAP (Applied Biosystems SCIEX) mass spectrometer. The HRMS mass spectral analysis was performed with a QStar Elite (Applied Biosystems SCIEX) mass spectrometer. Elemental analyses were recorded with a Thermo Finnigan EA 1112 elemental analysis apparatus driven by the Eager 300 software. 1 H and 13 C NMR spectra were determined at room temperature in 5 mm o. d. tubes on a Bruker Avance 400 spectrometer and on a Bruker Avance 300 spectrometer of the Spectropole: The 1 H chemical shifts were referenced to the solvent peak CDCl 3 (7.
Synthesis of the Coumarins All reagents and solvents were purchased from Aldrich, Alfa Aesar, or TCI Europe and used as received without further purification. Mass spectroscopy was performed by the Spectropole of Aix-Marseille University. ESI mass spectral analyses were recorded with a 3200 QTRAP (Applied Biosystems SCIEX) mass spectrometer. The HRMS mass spectral analysis was performed with a QStar Elite (Applied Biosystems SCIEX) mass spectrometer. Elemental analyses were recorded with a Thermo Finnigan EA 1112 elemental analysis apparatus driven by the Eager 300 software. mmol, M = 138. 12 g/mol) dissolved in absolute ethanol (30 mL). After stirring and heating to reflux for 6 hours, the solvent was removed under reduced pressure. Then, concentrated HCl (20 mL) and acetic acid (20 mL) were added for hydrolysis, and the solution was refluxed overnight.
and used as received without further purification. Mass spectroscopy was performed by the Spectropole of Aix-Marseille University. ESI mass spectral analyses were recorded with a 3200 QTRAP (Applied Biosystems SCIEX) mass spectrometer. The HRMS mass spectral analysis was performed with a QStar Elite (Applied Biosystems SCIEX) mass spectrometer. Elemental analyses were recorded with a Thermo Finnigan EA 1112 elemental analysis apparatus driven by the Eager 300 software. 1 H and 13 C NMR spectra were determined at room temperature in 5 mm o. d. tubes on a Bruker Avance 400 spectrometer and on a Bruker Avance 300 spectrometer of the Spectropole: The 1 H chemical shifts were referenced to the solvent peak CDCl3 (7. 26 ppm), and the 13 C chemical shifts were referenced to the solvent peak CDCl3 (77 ppm).