Structural rearrangement of Ag nanocluster endowing different luminescence performances.

It is well known that structure determines property, but obtaining a pair of silver nanoclusters with comparable structures to understand the structure-property relationship is a very challenging task. A new 60-nuclei silver nanocluster (SD/Ag60a) protected by a mixed-ligand shell of BuS and o-CHOPhCOO was obtained and characterized. Single crystal x-ray diffraction reveals that SD/Ag60a has an identical metal nuclearity and core-shell structural type to SD/Ag1 previously reported by our group, whereas the compositions of the core and shell have undergone a rearrangement from an Ag cuboctahedron core and an Ag rhombicuboctahedron shell in SD/Ag1 to an Ag rhombic dodecahedron core and an oval Ag shell in SD/Ag60a.

Thermally Hypsochromic or Bathochromic Emissions? The Silver Nuclei Does Matter.

Structural modulation of core-shell silver nanoclusters from the inside is a huge challenge but of great importance in their syntheses. Herein, two silver nanoclusters [Ag S @Ag ] (SD/Ag45b) and [Ag S @Ag ] (SD/Ag51a) are isolated in the presence of different kinds of sulfonic acids. Uniquely, SD/Ag45b and SD/Ag51a show typical core-shell structures with the similar Ag shell but different cores.

Keplerate Ag Cluster with 6 Silver and 14 Chalcogenide Octahedral and Tetrahedral Shells.

Silver clusters with more than 2 concentric silver shells are scarce. Here, we enable self-assembly and crystallize , a highly symmetric silver chalcogenide cluster (SCC) with 192 silver cations in 6 shells and 136 anionic groups in 14 shells. All but 1 of these 20 concentric shells are Platonic or Archimedean solids.

Carboxylic acid-tuned nickel(ii) clusters: syntheses, structures, solution behaviours and magnetic properties.

Three novel cicada-like nickel(ii) clusters, formulated as [Ni(bdped)(mba)(Hdmpz)(NO)(HO)]·4MeCN (SD/Ni6b), [Ni(bdped)(tca)(Hdmpz)(MeOH)(HO)]·MeOH (SD/Ni5a) and [Ni(Hbdped)(ba)(Hdmpz)]·2NO·2MeCN (SD/Ni4a), were obtained by tuning the auxiliary carboxylic acids, where Hbdped = 1,2-bis-(3,5-dimethylpyrazol-1-yl)-ethane-1,2-diol; Hmba = 2-methylbenzoic acid; Hdmpz = 3,5-dimethyl-1H-pyrazole; Htca = 3-thiophenecarboxylic acid; and Hba = benzoic acid. The structures of SD/Ni6b, SD/Ni5a and SD/Ni4a are built from a central NiO opened cube, appending two to zero NiNO octahedra. The solution behaviours of SD/Ni6b, SD/Ni5a and SD/Ni4a were studied in detail via an ESI-MS technique and their solution stabilities were confirmed.

Copper(II)-Assisted Ligand Fragmentation Leading to Three Families of Metallamacrocycle.

We present an unprecedented copper(II)-assisted organic ligand fragmentation process under basic conditions leading to several ligands within three families of metallamacrocycle, Cu, Cu, and Cu. The sequential multistep reaction include (i) the deprotonation of the starting alcohol, 1,2-bis(3,5-dimethyl-pyrazol-1-yl)ethane-1,2-diol () to its diolate followed by complexation through six bonds (μ) to three copper atoms in a ring, (ii) the breaking of the ethane-pyrazole C-N bonds by the different solvent alcohols to form 1-(3,5-dimethyl-pyrazol-1-yl)-2-methoxyethane-1,2-diolate () or 2-(3,5-dimethyl-pyrazol-1-yl)-2-hydroxyacetate (), while retaining coordination to the copper centers and (iii) the final step to ethane-1,1,2,2-tetraolate, CHO (). Importantly, the latter product, only observed on two previous occasions, occupies the core of Cu and Cu through exceptionally eight coordination bonds (μ).

Self-assembly of a nonanuclear Ni cluster via atmospheric CO fixation: synthesis, structure, collision-induced dissociation mass spectrometry and magnetic property.

A novel nonanuclear nickel(ii) cluster identified as [Ni9(OH)6(CO3)2(ba)8(Hdmpz)6(DMF)2]·EtOH·2DMF (SD/Ni9a, Hba = benzoic acid, Hdmpz = 3,5-dimethyl-1H-pyrazole) is successfully constructed from mixed ligands. The single-crystal X-ray diffraction (SCXRD) structural analysis confirms the composition and reveals the "drum-like" inner core structure surrounded by ba- and DMF. Six Hdmpz ligands in their neutral form further sandwich the "drum" up and down, and is hydrogen bonded with two carbonate anions that are derived from the atmospheric CO2 with the help of Et3N.

A Keplerian Ag nest of Platonic and Archimedean polyhedra in different symmetry groups.

Polyhedra are ubiquitous in chemistry, biology, mathematics and other disciplines. Coordination-driven self-assembly has created molecules mimicking Platonic, Archimedean and even Goldberg polyhedra, however, nesting multiple polyhedra in one cluster is challenging, not only for synthesis but also for determining the alignment of the polyhedra. Here, we synthesize a nested Ag nanocluster under solvothermal condition.

Unusual fcc-structured Ag kernels trapped in Ag nanoclusters.

Controlled trapping atom-precise ultrasmall silver nanoparticles into silver nanoclusters is challenging; thus only limited progress has been made in this area. We are therefore inspired to isolate two novel silver nanoclusters, Ag@Ag ( and ; SD = SunDi), where a novel fcc-structured Ag kernel built from two single-edge opened Ag octahedra by sharing one edge is trapped. The bioctahedral Ag kernel is locked by a pair of MoO anions to form an inner Ag@(MoO) core which is further encapsulated by an outer Ag shell to form three-shell Ag@(MoO)@Ag nanoclusters.

Three Silver Nests Capped by Thiolate/Phenylphosphonate.

Introducing phenylphosphonic acid (H PPA) into the Ag/tBuSH assembly system has produced a family of nanoscale-sized, high-atom number, silver thiolate/PPA nests (SD/Ag45 a, SD/Ag66 a, and SD/Ag73 a) with impressive core-shell features. SD/Ag45 a is a 45-atom ellipsoid comprised of an Ag shell trapping an Ag S three-bladed rotor inside. SD/Ag66 a comprises an inner rod-like Ag core and an outer Ag shell, giving a 64-atom nest.

Benzoate-Induced High-Nuclearity Silver Thiolate Clusters.

Compared with the well-known anion-templated effects in shaping silver thiolate clusters, the influence from the organic ligands in the outer shell is still poorly understood. Herein, three new benzoate-functionalized high-nuclearity silver(I) thiolate clusters are isolated and characterized for the first time in the presence of diverse anion templates such as S , α-[Mo O ] , and MoO . Single-crystal X-ray analysis reveals that the nuclearities of the three silver clusters (SD/Ag28, SD/Ag29, SD/Ag30) vary from 32 to 38 to 78 with co-capped tBuS and benzoate ligands on the surface.