Self-Assembly of an Anionic [Cu5I8]3- Supramolecular Cluster Driven by Ion-Pair Interaction and Catalytic Properties.

The rational design and controlling synthesis of an anionic cuprous iodide supramolecular cluster with high nuclearity through noncovalent interactions remains a significant challenge. Herein, a cationic organic ligand (L1)3+ was driven by anion-cation ion-pair electrostatic interaction to induce free cuprous iodide to aggregate into an anionic supramolecular cluster, [(Cu5I8)3-(L1)3+] (C1). Moreover, five copper(I) atoms bind with eight iodides through multiply bridged Cu-I bonds associated with intramolecular cuprophilic interactions in this butterfly-shaped cluster core. Supramolecular cluster C1 exhibited a solid-state emission at 380 nm and an emission at 405 nm in acetonitrile at room temperature, respectively. Interestingly, this unprecedented cuprous iodide cluster demonstrated a good catalytic performance for azide-alkyne cycloaddition reaction (CuAAC) and the catalytic yield can be up to 80% for eight different substrates at 80 °C. Furthermore, the density functional theory (DFT) calculation revealed that the thermodynamic-dependent cycloaddition reaction underwent a four-step pathway with an overall energy barrier of -43.6 kcal mol-1 on the basis of intermediates monitored by mass spectrum.

Self-Assembly of Mechanoluminochromic Ladder-Shaped Gold(I) Clusters Promoted Using Cooperative Aurophilicity.

The self-assembly of mechanoluminochromic polynuclear gold(I) complexes has attracted more and more attention in the field of supramolecular gold(I) chemistry. In this work, we adopted a stepwise self-assembly strategy to precisely synthesize two polynuclear gold(I) supramolecular clusters. Through cooperative AuI···AuI and Au-N interactions, the gold(I) clusters 1+•BF4- and 24+•4BF4- with Au4 and Au16 cores, respectively, were successfully constructed. In these supramolecular clusters, (dppm)Au2Cl2 coordination motifs and trithiocyanuric linkers were stepwise assembled via sequential thiolate-chloride/phosphine coordination substitution and Au-S/Au-N coordination bond rearrangement. Two well-defined gold(I) supramolecular clusters displayed intense emission both in the solid state and in solution. Furthermore, the ladder-shaped cluster 24+•4BF4- exhibited reversible mechanochromic luminescence behavior in the solid state as well as aggregation-caused redshifted emission in solution. Upon mechanical grinding, the emission of the cluster 24+•4BF4- changed from yellow at 582 nm to red at 612 nm. The initial emission could be fully recovered by treatment with acetonitrile.

[Responses of moss biocrusts respiration to simulated grazing and trampling disturbance with different intensities on the fenced forestland of Loess Plateau, China]. / 黄土高原封禁林地藓结皮呼吸速率对放牧踩踏干扰强度的响应.

The changes in soil properties caused by grazing and trampling are important reasons for the changes in soil respiration rates, carbon fixation, and emission. However, the effects of different intensities of grazing and trampling on biocrusts respiration rate are unclear. In this study, we simulated grazing and trampling disturbances of 10%, 30%, 50%, and 70% intensity on moss biocrusts developed in aeolian sandy soil on Loess Plateau, with undisturbed moss biocrusts serving as a control. The changes in respiration rate of moss biocrusts were monitored continuously, and its responses to different disturbance intensities were analyzed. The results showed that: 1) moderate disturbance stimulated moss biocrusts respiration, while heavy disturbance inhibited that. The respiration rate of moss biocrusts was increased by 41.1% and 22.2% at disturbance intensities of 10% and 30%, but was decreased by 8.9% and 15.3% at disturbance intensities of 50% and 70%, respectively. 2) The trampling disturbance significantly changed soil temperature but did not affect soil water content. In comparison to the control, soil temperature of biocrusts was decreased by 0.4 and 1.2 ℃ at disturbance intensities of 10% and 30%, but it was increased by 1.1 and 1.0 ℃ at disturbance intensities of 50% and 70%, respectively. 3) The respiration rate of moss biocrusts showed a significant exponential relationship with soil temperature and a linear positive relationship with soil water content under different disturbance intensities. However, the correlation between respiration rate of moss biocrust and the characteristics of moss biocrust was not significant. Soil temperature and water content could explain 70.6%-96.3% and 49.1%-70.0% of the total variation of respiration rate of moss biocrusts, respectively. In conclusion, grazing and trampling affected the respiration rate of moss biocrusts, with short-term moderate grazing and trampling would have positive effects. On the other hand, excessive grazing and trampling would reduce the rate of moss biocrust respiration. As a result, future studies on soil carbon balance of the Loess Plateau should consider the effects of grazing and trampling on biocrust respiration.

Superhydrophobic Porous Coating of Polymer Composite for Scalable and Durable Daytime Radiative Cooling.

Passive daytime radiative cooling (PDRC) technology provides an eco-friendly cooling strategy by reflecting sunlight reaching the surface and radiating heat underneath to the outer space through the atmospheric transparency window. However, PDRC materials face challenges in cooling performance degradation caused by outdoor contamination and requirements of easy fabrication approaches for scale-up and high cooling efficiency. Herein, a polymer composite coating of polystyrene, polydimethylsiloxane and poly(ethyl cyanoacrylate) (PS/PDMS/PECA) with superhydrophobicity and radiative cooling performance was fabricated and demonstrated to have sustained radiative cooling capability, utilizing the superhydrophobic self-cleaning property to maintain the optical properties of the coating surface. The prepared coating is hierarchically porous which exhibits an average solar reflectance of 96% with an average emissivity of 95% and superhydrophobicity with a contact angle of 160°. The coating realized a subambient radiative cooling of 12.9 °C in sealed air and 7.5 °C in open air. The self-cleaning property of the PS/PDMS/PECA coating helped sustain the cooling capacity for long-term outdoor applications. Moreover, the coating exhibited chemical resistance, UV resistance, and mechanical durability, which has promising applications in wider fields.