Pseudotetrahedral Organotin-Capped Chalcogenidometalate Supermolecules with Optical Limiting Performance.

The rational design of crystalline clusters with adjustable compositions and dimensions is highly sought after but quite challenging as it is important to understand their structural evolution processes and to systematically establish structure-property relationships. Herein, a family of organotin-based sulfidometalate supertetrahedral clusters has been prepared via mixed metal and organotin strategies at low temperatures (60-120 °C). By engineering the metal composition, we can effectively control the size of the clusters, which ranges from 8 to 35, accompanied by variable configurations: P1-[(RSn)4M4S13], T3-[(RSn)4In4M2S16] (R = nbutyl-Bu and phenyl-Ph; M = Cd, Zn, and Mn), T4-[(BuSn)4In13Cu3S31], truncated P2, viz. TP2-[(BuSn)6In10Cu6S31], and even T5-[(BuSn)4In22Zn6Cu3S52], all of which are the largest organometallic supertetrahedral clusters known to date. Of note, the arylstannane approach plays a critical role in regulating the peripheral ligands and further enriching geometric structures of the supertetrahedral clusters. This is demonstrated by the formation of tin-oxysulfide clusters, such as T3-[(RSn)4Sn6O4S16] (R = Bu, Ph, and benzyl = Be) and its variants, truncated T3, viz., TT3-[(BuSn)6Sn3O4S13] and augmented T3, viz., T3-[(Bu3SnS)4Sn6O4S16]. Especially, two extraordinary truncated clusters break the tetrahedral symmetry observed in typical supertetrahedral clusters, further substantiating the advantages offered by the arylstannane approach in expanding cluster chemistry. These organometallic supertetrahedral clusters are highly soluble and stable in common solvents. Additionally, they have tunable third-order nonlinear optical behaviors by controlling the size, heterometallic combination, organic modification, and intercluster interaction.

Superhydrophobic Pseudosupertetrahedral Sulfido Metalate Clusters for Constructing Liquid Marbles.

One pseudopentasupertetrahedral chalcogenidometalate cluster, [(BuSn)3SnCd4S13(OH)]·6(H+DMP) (PPS-1; H+DMP = protonated 3,5-dimethylpiperidine), has been isolated by use of an organotin precursor. They are arranged to generate two types of tetrahedrally patterned cages, which further interconnect to form a diamond network. Owing to the covalent attachment of abundant alkyl groups, PPS-1 exhibits excellent hydrophobicity and could be used as an assembly substance for building liquid marbles.

Modification of metallic and non-metallic sites in pentasupertetrahedral chalcogenidometalate clusters for third-order nonlinear optical response.

Four isomorphic P2 chalcogenide clusters named [Sn11In9Cu6S44]·11(H+DBU) (1) (DBU = 1,8-diazabicyclo[5.4.0] undec-7-ene), [Sn10In10Cu6Se44]·6(H22+DMAPA)·2(DMAPA)·9EG (2) (DMAPA = 3-dimethylaminopropylamine, EG = ethylene glycol), [Sn10In10Cu6S40O4]·6[H22+PMDETA]·10EG (3) (PMDETA = pentamethyldiethylenetriamine), [Sn10Ga10Cu6S40O4]·6(H22+DMAPA)·7EG (4) have been isolated via organotin precursor and mixed-metal strategy. These clusters exhibit excellent solubility in organic solvents. The continuous-regulation of optical band and optical limiting performance have been realized through precise controlled substituting engineering of cationic and anionic elements.

Photochemical In Situ Exfoliation of Metal-Organic Frameworks for Enhanced Visible-Light-Driven CO2 Reduction.

Two novel two-dimensional metal-organic frameworks (2D MOFs), 2D-M2 TCPE (M=Co or Ni, TCPE=1,1,2,2-tetra(4-carboxylphenyl)ethylene), which are composed of staggered (4,4)-grid layers based on paddlewheel-shaped dimers, serve as heterogeneous photocatalysts for efficient reduction of CO2 to CO. During the visible-light-driven catalysis, these structures undergo in situ exfoliation to form nanosheets, which exhibit excellent stability and improved catalytic activity. The exfoliated 2D-M2 TCPE nanosheets display a high CO evolution rate of 4174 µmol g-1 h-1 and high selectivity of 97.3 % for M=Co and Ni, and thus are superior to most reported MOFs. The performance differences and photocatalytic mechanisms have been studied with theoretical calculations and photoelectric experiments. This study provides new insight for the controllable synthesis of effective crystalline photocatalysts based on structural and morphological coregulation.

Tin-oxychalcogenide supertetrahedral clusters maintained in a MTN zeolite-analog arrangement by coulombic interactions.

Two crystalline salts, T3-SnOX-MTN (X = S/Se, MTN denotes a defined zeotype), both spatially assembled in an MTN net, have been fabricated. This was achieved by interlinking the isolated tin-oxychalcogenide tetrahedrally shaped clusters of T3-[Sn10O8X16]8- (X = S/Se) through coulombic interactions with protonated organic amine templates. T3-SnOX-MTN (X = S/Se), with 74.1/76.5 Å cubic unit-cell axial-lengths, have a proton-conductivity of over 10-3 S cm-1 under 98% relative humidity at 50 °C.