The syntheses and structures of a [2×1+1×2] cocrystal [{Cu II L 1 Na I (H 2 O) 2 }{Cu II L 1 } 2 ](NO 3 ) (1) and [3×1+5×1] cocrystal [{(Cu II L 1 ) 2 K I }(NO 3 )] • [{(Cu II L 1 ) 3 K I 2 (µ-NO 3 )}(NO 3 )] • 0.2H 2 O (2) derived from the hexadentate Schiff base compartmental ligand N,N′-ethylenebis(3-ethoxysalicylaldimine) (H 2 L 1 ) are described. Compounds 1 and 2 crystallize in triclinic P1 j and monoclinic P2 1 /c systems, respectively. The structure of 1 consists of the [Cu II L 1 Νa I (H 2 O) 3 ] + cation and two mononuclear [Cu II L 1 ] moieties. In the dinuclear [Cu II L 1 Νa I (H 2 O) 3 ] + cation, the metal centers are doubly bridged by the two phenolate oxygen atoms. Each of the two coordinated water molecules of the dinuclear unit is encapsulated in the O 4 cavities of the two mononuclear [Cu II L 1 ] moieties resulting in the formation of a [2×1+1×2] cocrystal. In compound 2, one trinuclear double-decker system [{(Cu II L 1 ) 2 K I }(NO 3 )] and one pentanuclear triple-decker system [{(Cu II L 1 ) 3 K I 2 (µ-NO 3 )}(NO 3 )] are cocrystallized. Evidently, compound 2 is a [3×1+5×1] cocrystal. Structural resemblance of 3d metal ions with Na(I) and a rare example of double-decker-triple-decker cocrystal are the major outcomes of the present investigation.

Under the shielding effect of nanomicelles, a sustainable micellar technology for the design and convenient synthesis of ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) and their subsequent catalytic exploration for couplings of water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays a crucial role in stabilizing these NPs, preventing their aggregation and oxidation state changes. These NPs were characterized using 13 C nuclear magnetic resonance (NMR), infrared (IR), and surface-enhanced Raman scattering (SERS) spectroscopy to evaluate the carbonyl interactions of PS-750-M with Pd. High-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDX) studies were performed to reveal the morphology, particle size distribution, and chemical composition, whereas X-ray photoelectron spectroscopy (XPS) measurements unveiled the oxidation state of the metal. In the cross-couplings of water-sensitive acid chlorides with boronic acids, the micelle’s shielding effect and boronic acids plays a vital role in preventing unwanted side reactions, including the hydrolysis of acid chlorides under basic pH. This approach is scalable and the applications are showcased in multigram scale reactions.

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The single crystal structure analysis reveals that compound H 2 L1 crystallized in its salt form H 3 L1 + Cl -, obtained upon addition of dilute HCl into a methanolic solution of H 2 L1. The pyridyl N-atom of H 2 L1 was protonated and the cationic charge of the ligand was balanced by the negative charge of the chloride anion (Figure 1A). The pyridine and isophthalate units are in different planes which make an angle of 72.97 o , the C4-N1-C9-C10 torsional angle being -87.64 o . One of the carboxylic groups of H 3 L1 + is engaged in extensive strong R 2 2 (8) type O4-H4••••O3 (d D-A 2.652(3) Å,