We report the synthesis and crystal structure of a nanocluster composed of 23 silver atoms capped by 8 phosphine and 18 phenylethanethiolate ligands. X-ray crystallographic analysis reveals that the kernel of the Ag nanocluster adopts a helical face-centered cubic structure with C2 symmetry. The thiolate ligands show two binding patterns with the surface Ag atoms: tri- and tetra-podal types. The tetra-coordination mode of thiolate has not been found in previous Ag nanoclusters. No counter ion (e.g., Na+ and NO3−) is found in the single-crystal and the absence of such ions is also confirmed by X-ray photoelectron spectroscopy analysis, indicating electrical neutrality of the nanocluster. Interestingly, the nanocluster has an open shell electronic structure (i.e., 23(Ag 5s1)–18(SR) = 5e), as confirmed by electron paramagnetic resonance spectroscopy. Time-dependent density functional theory calculations are performed to correlate the structure and optical absorption/emission spectra of the Ag nanocluster.

Supplementary Figures and Tables Figure S1. Scheme of dataset splitting through randomly training/test splitting and hyperparameter tuning via 5-fold GridSearchCV. This process was repeated 5 times through changing random seed and the average of evaluation metrics was reported.

A sequential postsynthetic ligand exchange process was used to prepare a series of mono-, di-, and trifunctionalized mesoporous metal-organic frameworks (MOFs). Using this process, orthogonal functional groups were installed and thereafter postsynthetically modified with dye and quencher molecules. Microspectrophotometry studies were used to determine the distribution of the two orthogonal functional groups within the MOF crystals.

The two-dimensional framework of nickel-seamed hexameric metal-organic nanocapsules has been synthesized by connecting the tailed hydroxyl groups of C-propan-3-ol pyrogallol[4]arene with adjacent hexameric capsules via nickel-hydroxyl coordination. In addition, functionalization of nanocapsules with multiple pyridine molecules at the capsule surface prevents them from assembling into hierarchical structures and leads to the formation of discrete nickel-seamed pyrogallol[4]arene nanocapsules. This work shows that surface functionalization of nanocapsules is an effective and innovative method of controlling the assembly of these nanometric building blocks.