Nonlinear time effects of vegetation response to climate change: Evidence from Qilian Mountain National Park in China.

Vegetation responses to climate change are typically nonlinear with varied time effects, yet current research lacks comprehensiveness and precise definitions, hindering a deeper understanding of the underlying mechanisms. This study focuses on the mountain-type Qilian Mountain National Park (QMNP), investigating the characteristics and patterns of these nonlinear time effects using a generalized additive model (GAM) based on MODIS-NDVI, growing season temperature, and precipitation data. The results show that 1) The time effects of climate change on vegetation exhibit significant spatial variations, differing across vegetation types and topographic conditions. Accounting for optimal time effects can increase the explanatory power of climate on vegetation change by 6.8 %. Precipitation responses are mainly characterized by time-lag and time-accumulation effects, notably in meadows and steppes, while temperature responses are largely cumulative, especially in steppes. The altitude and slope significantly influence the pattern of vegetation response to climate, particularly in areas with high altitudes and steep slopes. 2) There is a significant nonlinear relationship between vegetation growth and both precipitation and temperature, with the nonlinear relationship between precipitation and vegetation being stronger than that with temperature, particularly in the western and central regions of the park. Different vegetation types exhibit significant variations in their response to climate change, with deserts and steppes being more sensitive to precipitation. 3) Precipitation is the primary driver of vegetation change in the QMNP, particularly for high-elevation vegetation and herbaceous vegetation. The complex temporal patterns of vegetation response to climate change in the QMNP not only deepen the understanding of the intricate relationship between regional vegetation and climate variability but also provide a methodological reference for global studies on vegetation responses to climate change.

Synergetic Spin-Crossover and Luminescent Properties in a Multifunctional 2D Iron(II) Coordination Polymer.

We designed and synthesized a strong fluorescent tetradentate pyridine ligand, 3,6,11,12-tetra(pyridin-4-yl)dibenzo[a,c]phenazine (TPDP), by covalently grafting pyridyl to fluorescent dye dbpz, which can react with the Fe(NCX)2 (X = S and Se) unit, obtaining two new 2D [4 × 4] square-grid compounds, namely, {FeII(TPDP)2(SCN)2·CHCl3·4CH3OH}n (1) and {[FeII(TPDP)2(SeCN)2]·CH2Cl2·4CH3OH}n (2). Both of them show expected one-step spin-crossover (SCO) properties, and complex 2vacuum exhibits a combination of the SCO phenomenon and fluorescence in a synergetic way. The energy transfer mechanism of 2vacuum is verified by the theoretical calculations and experimental results. This study provides an effective strategy to synthesize large conjugated fluorescent ligands using dyes to further form SCO-luminescent bifunctional materials.

Single-molecule magnet behaviour in a centrosymmetric dinuclear dysprosium(III) complex: sequential differentiation of triple relaxation pathways.

A dinuclear complex with the formula Dy2L2(H2L)Cl2(EtOH)2 (Dy2) has been synthesized by reacting DyCl3·H2O with a ligand H2L (H2L = N,N'-ethylenebis(salicylideneimine)) using ethanol as the solvent. Its crystal structure can be viewed as a dimer of two Dy(III) fragments, where each Dy(III) site shows a N2O6Cl coordination sphere with a pentagonal bipyramid geometry (D5h). Magnetic measurements reveal that Dy2 behaves as a single-ion magnet (SIM) under a zero field. When the field is applied, the ac magnetic susceptibilities show double and triple peaks under high (≥600 Oe) and low (<600 Oe) dc fields, respectively. In contrast to the common double relaxation pathways in SIMs, such multiple and intricate relaxation pathways have not been reported yet in the previous literature. In this work, by experimental analysis of the ac signals, we attribute the three slow relaxation pathways to quantum tunnelling of magnetization (QTM), intermolecular dipole-dipole interaction and spin reversal, respectively. In addition, ab initio calculations are used to elucidate the magnetic behaviours of Dy2. Overall, our work indicates that the interpretation of the relaxation process using double relaxation pathways is incomplete and difficult in previously reported literature.

Microstructure Evolution and Toughening Mechanism of a Nb-18Si-5HfC Eutectic Alloy Created by Selective Laser Melting.

Because of their superior mechanical performance at ultra-high temperatures, refractory niobium-silicon-based alloys are attractive high-temperature structural alloys, particularly as structural components in gas turbine engines. However, the development of niobium-silicon-based alloys for applications is limited because of the trade-off between room temperature fracture toughness and high-temperature strength. Here, we report on the fabrication of a Nb-18Si alloy with dispersion of hafnium carbide (HfC) particles through selective laser melting (SLM). XRD and SEM-BSE were used to examine the effects of scanning speed on the microstructure and the phase structure of the deposited Nb-18Si-5HfC alloy. The results show that when the scanning speed rises, the solid solubility of the solid solution improves, the interlamellar spacing of eutectics slowly decrease into nano-scale magnitude, and the corresponding hafnium carbide distribution becomes more uniform. We also discover the hafnium carbide particles dispersion in the inter-lamella structure, which contributes to its high fracture toughness property of 20.7 MPa∙m1/2 at room temperature. Hardness and fracture toughness are simultaneously improved because of the control of microstructure morphology and carbide distribution.

Reversible Switching of Single-Molecule Magnetic Behaviour by Desorption/Adsorption of Solvent Ligand in a New Dy(III)-Based Metal Organic Framework.

Two metal-organic frameworks (MOFs), [Dy(BDC)(NO3)(DMF)2] n (1, H2BDC = terephthalic acid) and [Dy(BDC)(NO3)] n (1a), were synthesized. The structures of MOFs 1 and 1a are easy to be reversibly transformed into each other by the desorption or adsorption of coordination solvent molecules. Accordingly, their magnetic properties can also be changed reversibly, which realizes our goals of manipulating on/off single-molecule magnet behaviour. MOF 1 behaves as a single-molecule magnet either with or without DC field. Contrarily, no slow magnetic relaxation was observed in 1a both under zero field and applied field.

Structurally modulated single-ion magnets of mononuclear ß-diketone dysprosium(III) complexes.

Five ß-diketone based Dy(iii) single-ion magnets (SIMs), [DyIII(TTA)3(AIP)]·0.5CH3CH2OH·0.5H2O (1), [DyIII(TTA)3(APIP)]·2CH3OH·H2O (2), [DyIII(TTA)3(DPP)] (3), [DyIII(TTA)3(BPP)]·0.5CH3CH2OH (4) and [DyIII(TTA)3(AIP)]·1.5H2O (5), were fully synthesized through alteration of their phenanthroline derivates (AIP = 2-(anthracen-9-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, APIP = 2-(4-(anthracen-9-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, DPP = 2,3-diphenylpyrazino[2,3-f][1,10]phenanthroline and BPP = 2,3-bis(2,5-dimethylthiophen-3-yl)pyrazino[2,3-f][1,10]phenanthroline). Magnetic investigations reveal that all the complexes perform as SIMs, with notably different effective barriers of 69.4 K (1), 147.3 K (2), 122.1 K (3) and 234.2 K (4) in zero direct current (dc) field. Complexes of 2 and 4 possess almost twofold higher effective barriers compared to 1 and 3. By analyzing the crystal structures, the distinct magnetic dynamics was found to stem from the variation in intermolecular hydrogen bond interactions and charge delocalization of auxiliary ligands. With the help of ab initio calculations, a change of auxiliary ligand brings about varying intensities of quantum tunnelling magnetization (QTM), which account for the distinguishable magnetic dynamics. With a combination of experimental and theoretical analyses, this work provides a visual and instructive perspective to the understanding of fine tuning auxiliary ligands to design structurally modulated SIMs of mononuclear ß-diketone dysprosium(iii) complexes.

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double µ-Phenoxo Bridges.

A new µ-phenoxo-bridged dinuclear cobalt(II) complex, [Co2(L)2(acac)2(H2O)] (1), has been synthesized by employing a new ligand, (4-methyl-2-formyl-6-(((2-trifluoromethyl)phenyl)methyliminomethyl) phenol) (HL). Structural analysis of complex 1 reveals that the geometry around cobalt centers is best described as a distorted octahedron and the distance of cobalt neighbors is 3.128(0) Å. The magnetic property studies indicate that complex 1 exhibits strong spin-orbit coupling effects and weak ferromagnetic coupling between two high-spin Co(II) centers linked by double µ-Ophenoxo bridges, with J = 1.87(2) cm-1. The studies show that not only the Co-O-Co angle affects the alignment of the cobalt spins but also the dihedral angle between the CoOCo plane and the phenyl plane plays an important role in the magnetic coupling in this [Co2O2] system. Thus, the small bridging angles (96.96(11) and 96.91(11)°) and the large dihedral angles between the CoOCo plane and the phenyl plane (63.0(1) and 30.6(1)°) induce intramolecular ferromagnetic exchange interaction in complex 1.

Assembling 1D magnetic chain based on octacyanotungstate(V) and [Cu2L2Ln] sub-building units (Ln = Eu, Gd, Tb and Dy).

Reaction of (NBu3H)3[W(CN)8]·H2O and linear trinuclear complexes [Cu(II)2L2Ln(III)(NO3)3] (L = 2,6-di(acetoacetyl)pyridine, Ln = Eu (1), Gd (2), Tb (3) and Dy (4)) leads to the formation of four one-dimensional (1D) complexes. Single crystal X-ray analysis reveals that [W(CN)8](3-) bridges between the [Cu(II)2L2Ln(III)] sub-building units to construct the alternative chains. Magnetic investigation indicates that ferromagnetic interaction occurred between all paramagnetic ions and the slow magnetic relaxation properties were observed in complexes 3 and 4.

Preparation and characterization of a polystyrene/bovine serum albumin nanoparticle-coated capillary for chiral separation using open-tubular capillary electrochromatography.

Polystyrene (PS) nanoparticles coated by BSA, hereafter denoted as PS/BSA, were prepared and chemically immobilized for the first time onto a capillary inner wall for open-tubular CEC (OTCEC). EOF and scanning electron micrography were used to characterize the prepared nanoparticle-coated capillaries. To investigate the performance of the prepared columns in OTCEC, chiral separation of d,l-tryptophan (dl-Trp) was performed in monolayer BSA-modified capillary and PS/BSA nanoparticle-coated columns. The results indicated that the nanoparticle-modified column afforded a higher resolution compared with the monolayer type. Rapid enantioseparation of dl-Trp (within 3 min) was achieved with the PS/BSA-immobilized column using an electroosmotic pump-assisted CEC. Enantiomer separations of other compounds like dl-tyrosine and warfarin were also achieved with the column. Besides, run-to-run and column-to-column repeatabilities of the PS/BSA-coated column in the chiral separation were systematically introduced.

Magnetic properties of two 2D complexes based on 1D chain containing [Fe(bpy)(CN)4]- unit.

Two heterobimetallic 2-dimensional layer complexes, {[Fe(bpy)(CN)(4)](2)M(4,4'-bipyridine)}·4H(2)O [bpy = 2,2'-bipyridine, M = Mn (1), Cu (2)] have been prepared by diffusion and their structures determined by single crystal X-ray diffraction. 1 and 2 are isomorphous, made of neutral bimetallic [Fe(bpy)(CN)(4)](2)M(4,4'-bipyridine)] layers and uncoordinated water molecules located between the layers. Interestingly, complex 2 shows the compression of the Jahn-Teller distortion around the copper(II) ion. Magnetic investigation shows antiferromagnetic coupling between the manganese(II) and iron(III) ions mediated by bridging CN(-) in 1, while ferromagnetic coupling between the copper(II) and iron(III) ions is seen in 2. Both complexes 1 and 2 reveal a metamagnetic-like behaviour with different critical fields (H(c), at 1.8 K): 2.0 kOe (1) and 3.2 kOe (2). The weak interchain antiferromagnetic interaction can be illustrated by the spin-polarization mechanism.

Formation of stable iron/cobalt NHC complexes via unexpected ring opening and in situ generation of a tridentate ligand.

The reactions of FeCl(2) and CoCl(2) with a bistriazolium salt yields the NHC complexes [Fe(III)(L1)(2)]I·H(2)O, [Fe(III)(L2)(2)]PF(6)·CH(3)CN and [Co(III)(L1)(2)]I·0.5CH(3)CN, through an unusual ring opening of one of the triazoyl rings, which leads to the formation of C,N,O tridentate ligands L1 or L2. Furthermore, a Fe(ii) species [Fe(II)(L1)(2)]·CH(2)Cl(2) was also obtained.

Synthesis, structure, and magnetic properties of three 1D chain complexes based on high-spin metal-cyanide clusters: [Mn(III)6M(III)] (M = Cr, Fe, Co).

On the basis of high-spin metal-cyanide clusters of Mn(III)(6)M(III) (M = Cr, Fe, Co), three one-dimensional (1D) chain complexes, [Mn(salen)](6)[Cr(CN)(6)](2)·6CH(3)OH·H(2)O (1), [Mn(5-CH(3))salen)](6)[Fe(CN)(6)](2)·2CH(3)CN·10H(2)O (2), and [Mn(5-CH(3))salen)](6)[Co(CN)(6)](2)·2CH(3)CN·10H(2)O (3) [salen = N,N'-ethylenebis(salicylideneiminato) dianion], have been synthesized and characterized structurally as well as magnetically. Complexes 2 and 3 are isomorphic but slightly different from complex 1. All three complexes contain a 1D chain structure which is comprised of alternating high-spin metal-cyanide clusters of [Mn(6)M](3+) and a bridging group [M(CN)(6)](3-) in the trans mode. Furthermore, the three complexes all exhibit extended 3D supramolecular networks originating from short intermolecular contacts. Magnetic investigation indicates that the coupling mechanisms are intrachain antiferromagnetic interactions for 1 and ferromagnetic interactions for 2, respectively. Complex 3 is a magnetic dilute system due to the diamagnetic nature of Co(III). Further magnetic investigations show that complexes 1 and 2 are dominated by the 3D antiferromagnetic ordering with T(N) = 7.2 K for 1 and 9.5 K for 2. It is worth noting that the weak frequency-dependent phenomenon of AC susceptibilities was observed in the low-temperature region in both 1 and 2, suggesting the presence of slow magnetic relaxations.

Synthesis, structure, magnetic properties and DFT calculations of two hydroxo-bridged complexes based on Mn(III)(Schiff-Bases).

Two hydroxo-bridged complexes, {[Mn(III)(3-CH(3)O)salen](2)[Cr(III)(salen)(OH)(2)]}ClO(4)·6H(2)O (1) and {[Mn(III)(5-CH(3))salen](2)(OH)}ClO(4)·3H(2)O (2) [salen = N,N'-ethylenebis(salicylideneiminato) dianion], have been synthesized by the hydrolysis of the corresponding Mn(III)(Schiff-Bases) derivatives and [Cr(salen)(H(2)O)(2)]Cl precursors. X-Ray structure characterization reveals the discrete linear arched trinuclear structure of 1 and the 1D chain arrangement of 2. Magnetic experimental data and density functional theory (DFT) calculations both indicate the dominant antiferromagnetic interaction mediated by the hydroxo-bridges in both 1 and 2. Frequency-dependent AC susceptibilities reveal slow relaxation of 1 in low temperature. It is worth noting that the structure and magnetic properties of 1 is comparable to a reported cyano-bridged SMM, K[(5-Brsalen)(2)(H(2)O)(2)Mn(2)Cr(CN)(6)]·2H(2)O.

New high-nuclearity manganese clusters containing mixed chelating ligands: syntheses, crystal structures and magnetochemical characterization.

Two polynuclear mixed-valence manganese clusters, [Mn(13)] and [Mn(16)], containing mixed chelating ligands were synthesized and structurally characterized. The alternating current (AC) susceptibilities of both complexes reveal nonzero frequency-dependent out-of-phase (χ(M)'') signals.

Octacyanotungstate(v)-based square W(2)M(2) (M = Co, Mn) complexes: synthesis, structure and magnetic properties.

The preparation, single-crystal X-ray crystallography and magnetic properties are reported for two tetranuclear cluster complexes based on [W(V)(CN)(8)](3-) octacyanometallates. Reactions of [W(V)(CN)(8)](3-) with Co(II) ions in the presence of the capping ligand tpm (tpm = tri(1H-pyrazol-1-yl)methane) lead to the formation of complex 1 [(tpm)(2)Co(II)][W(V)(2)(CN)(16)Co(2)(tpm)(2)(H(2)O)(2)].4H(2)O. Analogous reactions with the Mn(II) produce complex 2 [(tpm)(2)Mn(II)][W(V)(2)(CN)(16)Mn(2)(tpm)(2)(H(2)O)(2)].4H(2)O. Complexes 1 and 2 are isomorphous and crystallize in the space group of P1[combining macron]. Magnetic investigation shows the ferromagnetic coupling between Co(II) and W(V) ion in complex 1, while the antiferromagnetic interactions between Mn(II) and W(V) in complex 2. Further magnetic studies indicate the presence of spin glasses in complex 2, which may be attributed to the further ferromagnetic coupling between anionic and/or cationic cores.