Boosting photothermal conversion through array aggregation of metalloporphyrins in bismuth-based coordination frameworks.

Materials capable of efficiently converting near-infrared (NIR) light into heat are highly sought after in biotechnology. In this study, two new three-dimensional (3D) porphyrin-based metal-organic frameworks (MOFs) with a -net, CoTCPP-Bi/NiTCPP-Bi, were successfully synthesized. These MOFs feature bismuth carboxylate nodes interconnected by metalloporphyrinic spacers, forming one-dimensional (1D) arrays of closely spaced metalloporphyrins.

Regulating electron transfer and orbital interaction within metalloporphyrin-MOFs for highly sensitive NO sensing.

The understanding of electron transfer pathways and orbital interactions between analytes and adsorption sites in gas-sensitive studies, especially at the atomic level, is currently limited. Herein, we have designed eight isoreticular catechol-metalloporphyrin scaffolds, FeTCP-M and InTCP-M (TCP = 5,10,15,20-tetrakis-catechol-porphyrin, M = Fe, Co, Ni and Zn) with adjustable charge transfer schemes in the coordination microenvironment and precise tuning of orbital interactions between analytes and adsorption sites, which can be used as models for exploring the influence of these factors on gas sensing. Our experimental findings indicate that the sensitivity and selectivity can be modulated using the type of metals in the metal-catechol chains (which regulate the electron transfer routes) and the metalloporphyrin rings (which fine-tune the orbital interactions between analytes and adsorption sites).

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)MS], T3-[(RSn)InMS] (R = butyl-Bu and phenyl-Ph; M = Cd, Zn, and Mn), T4-[(BuSn)InCuS], truncated P2, viz.

Multilevel-Regulated Metal-Organic Framework Platform Integrating Pore Space Partition and Open-Metal Sites for Enhanced CO Photoreduction to CO with Nearly 100% Selectivity.

Rational design and regulation of atomically precise photocatalysts are essential for constructing efficient photocatalytic systems tunable at both the atomic and molecular levels. Herein, we propose a platform-based strategy capable of integrating both pore space partition (PSP) and open-metal sites (OMSs) as foundational features for constructing high-performance photocatalysts. We demonstrate the first structural prototype obtained from this strategy: pore-partitioned NiTCPE- (TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, = partitioned topology).

Superhydrophobic Pseudosupertetrahedral Sulfido Metalate Clusters for Constructing Liquid Marbles.

One pseudopentasupertetrahedral chalcogenidometalate cluster, [(BuSn)SnCdS(OH)]·6(HDMP) (PPS-1; HDMP = 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.

Accurate binding of porous aluminum molecular ring catalysts with the substrate.

Metal molecular rings are a class of compounds with aesthetically pleasing symmetry and fundamentally useful properties. The reported work generally focuses on the ring center cavity, and there is little known about those on the ring waist. Herein, we report the discovery of porous aluminum molecular rings and their performance and contribution to the cyanosilylation reaction.

Thiophenol-spaced 2D coordination polymers with extraordinary alkali resistance and efficient photothermal conversion.

Coordination polymers (CPs) based on metal-sulfur bonds are rare; we herein realize a series of thiol-functionalized linker-based CPs (thiol-CPs), MTBT (M = Fe, Co and Zn; TBT = dehydrated 4,4'-thiobisbenzenethiol), which feature an anionic two-dimensional (2D) network, [M(TBT)], with the tetrahedral coordination unit {MS} serving as a node. These compounds exhibit excellent hydrolytic stability, especially in alkaline solution (20M NaOH for five days), which is the highest value reported for CPs so far. In addition, among them, CoTBT displays favorable photo-thermal conversion effectiveness under an energy power of 0.

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

Four isomorphic P2 chalcogenide clusters named [SnInCuS]·11(HDBU) (1) (DBU = 1,8-diazabicyclo[5.4.0] undec-7-ene), [SnInCuSe]·6(HDMAPA)·2(DMAPA)·9EG (2) (DMAPA = 3-dimethylaminopropylamine, EG = ethylene glycol), [SnInCuSO]·6[HPMDETA]·10EG (3) (PMDETA = pentamethyldiethylenetriamine), [SnGaCuSO]·6(HDMAPA)·7EG (4) have been isolated organotin precursor and mixed-metal strategy.

Energy Band Alignment and Redox-Active Sites in Metalloporphyrin-Spaced Metal-Catechol Frameworks for Enhanced CO Photoreduction.

Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO -scaffold affinity.

Construction of Titanium-Based Metal-Organic Frameworks Based on the Ti/Cu Heteronuclear Cluster.

Presented here are two titanium-based metal-organic frameworks (Ti-MOFs) based on well-defined [TiCu(μ-O)(μ-O)(HSO)(SO)], which can be easily obtained from a cheap Ti source and CuSO and exhibited interesting magnetic properties. Furthermore, this clusters can be isolated in pure phase. Numerous uncoordinated sites of SO and labile ligands on the Ti and Cu centers of this cluster make it a good candidate as a secondary building unit to construct various Ti-MOFs in the future.

Understanding the Efficiency and Selectivity of Two-Electron Production of Metalloporphyrin-Embedded Zirconium-Pyrogallol Scaffolds in Electrochemical CO Reduction.

Because of the high efficiency and mild reaction conditions, electrocatalytic CO reduction (ECR) has attracted significant attention in recent years. However, the specific mechanism of the formation of the two-electron production (CO or HCOOH) in this reaction is still unclear. Herein, with density functional theory calculation and experimental manipulation, the specific mechanism of the selective two-electron reduction of CO has been systematically investigated, employing the polyphenolate-substituted metalloporphyrinic frameworks, ZrPP-1-M (M = Fe, Co, Ni, Cu, and Zn), as model catalysts.

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

Two novel two-dimensional metal-organic frameworks (2D MOFs), 2D-M 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 CO 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-M TCPE nanosheets display a high CO evolution rate of 4174 μmol g  h and high selectivity of 97.

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.

Elucidating J-Aggregation Effect in Boosting Singlet-Oxygen Evolution Using Zirconium-Porphyrin Frameworks: A Comprehensive Structural, Catalytic, and Spectroscopic Study.

Metal-organic frameworks (MOFs) are powerful toolkits to directly correlate structure-function relationships due to their well-defined structures. In this work, 5,15-di(3,4,5-trihydroxyphenyl)porphyrin (DTPP) and 5,10,15,20-tetra(3,4,5-trihydroxyphenyl)porphyrin (TTPP) are reacted with zirconium ions to afford two MOFs (Zr-DTPP and Zr-TTPP) with acid and base tolerance in the pH range of 1.0-14.

A wide pH-range stable crystalline framework based on the largest tin-oxysulfide cluster [SnOS].

We report, herein, a diamond-like oxysulfide framework, 3D-T4-SnOS, based on the largest supertetrahedral cluster of Sn ions, i.e. [SnOS].

Robust Porphyrin-Spaced Zirconium Pyrogallate Frameworks with High Proton Conduction.

An isoreticular family of zirconium polyphenolate networks (ZrPP- n, n = 1 and 2), bridged by porphyrinic macrocycles in an eclipsed arrangement, have excellent stability toward water, especially strong basic media of saturated NaOH aqueous solution. Endowed with spatial alignment of protic sites, viz., partially protonated phenols of acidity enhanced by coordination to Zr, along with guest dimethylamine cations, the newly synthesized ZrPP- n reveal exceptional conductivity (8.

Dual-cubic-cage based lanthanide sulfate-carboxylpyrazolate frameworks with high hydrolytic stability and remarkable proton conduction.

We report herein a series of lanthanide sulfate-carboxylpyrazolate frameworks based on double cuboid cavities that are highly hot-water stable, and have room-temperature proton conductivity of over 10-3 S cm-1 at 97% relative humidity without any appreciable loss of performance for at least three recycling times, ranking among the best lanthanide-based coordination frameworks.

Robust multivariate metal-porphyrin frameworks for efficient ambient fixation of CO to cyclic carbonates.

A family of multivariate metal-organic frameworks (MOFs) with three-kinds of orderly distributed metals were designed and successfully synthesized by combining metalloporphyrin sheets and pentafluoride (NbOF5)2- pillars. Benefiting from the cooperative nature of open-metal-sites (OMSs) within porphyrins, specific pore-sizes, coupled with fluorine-rich electrostatic environments, the fabricated materials demonstrated high affinity toward CO2, and good catalytic performance, structural robustness, and good recyclability for the conversion of epoxides and CO2 to cyclic carbonates at room temperature and 1 atm pressure.

Charge- and Size-Complementary Multimetal-Induced Morphology and Phase Control in Zeolite-Type Metal Chalcogenides.

Zeolite-type chalcogenides are desirable due to their integration between porosity and semiconductivity. CPM-120, with super-sodalite topology (Zeolite Structure Code: RWY), is among the few zeolite-type chalcogenides with permanent porosity, and is the only chalcogenide with a zeolite code. Importantly, the RWY-type has evolved into a platform for studying properties of porous chalcogenides.

Acid and Base Resistant Zirconium Polyphenolate-Metalloporphyrin Scaffolds for Efficient CO Photoreduction.

A series of zirconium polyphenolate-decorated-(metallo)porphyrin metal-organic frameworks (MOFs), ZrPP-n (n = 1, 2), featuring infinite Zr -oxo chains linked via polyphenolate groups on four peripheries of eclipse-arranged porphyrin macrocycles, are successfully constructed through a top-down process from simulation to synthesis. These are the unusual examples of Zr-MOFs (or MOFs in general) based on phenolic porphyrins, instead of commonly known carboxylate-based types. Representative ZrPP-1 not only exhibits strong acid resistance (pH = 1, HCl) but also remains intact even when immersed in saturated NaOH solution (≈20 m), an exceptionally large range of pH resistance among MOFs.

Integrating Zeolite-Type Chalcogenide with Titanium Dioxide Nanowires for Enhanced Photoelectrochemical Activity.

Developing photoanodes with efficient visible-light harvesting and excellent charge separation still remains a key challenge in photoelectrochemical water splitting. Here zeolite-type chalcogenide CPM-121 is integrated with TiO nanowires to form a heterostructured photoanode, in which crystalline CPM-121 particles serve as a visible light absorber and TiO nanowires serve as an electron conductor. Owing to the small band gap of chalcogenides, the hybrid electrode demonstrates obvious absorption in visible-light range.

Water-Soluble and Ultrastable TiL Tetrahedron with Coordination Assembly Function.

We have successfully constructed a tetrahedral TiL cage with calixarene-like coordination-active vertices. It further features high solubility and stability in HO and DMF/HO solution, affording an interesting stepwise assembly function with other metal ions. Through trapping of different amounts of Co or Ln ions, the TiL tetrahedra can be organized into various dimensional architectures, including a TiL-Co cage, a TiL-Ln cage, a TiL-Ln chain, and a three-dimensional TiL-Ln framework.

Selective Ion Exchange and Photocatalysis by Zeolite-Like Semiconducting Chalcogenide.

The development of novel photocatalysts usually centers on features such as band structures, various nano-, micro-, or macro-forms, and composites in efforts to tune their light absorption and charge separation efficiency. In comparison, the selectivity of photocatalysts with respect to features of reactants such as size and charge has received much less attention, in part due to the difficulty in designing semiconducting photocatalysts with uniform pore size. Here, we use crystalline porous chalcogenides as a platform to probe reactant selectivity in photocatalytic processes.

Nanoporous carbon derived from a functionalized metal-organic framework as a highly efficient oxygen reduction electrocatalyst.

High levels of iron-nitrogen doped porous carbon materials are obtained from MOF-253 using a step-by-step post-synthetic modification strategy. MOF-253 possessing open 2,2'-bipyridine nitrogen sites not only serves as a precursor but also provides chelate bonding sites for Fe. Followed by further impregnation of 1,10-phenanthroline, high surface area porous carbon materials are obtained.

Open framework metal chalcogenides as efficient photocatalysts for reduction of CO2 into renewable hydrocarbon fuel.

Open framework metal chalcogenides are a family of porous semiconducting materials with diverse chemical compositions. Here we show that these materials containing covalent three-dimensional superlattices of nanosized supertetrahedral clusters can function as efficient photocatalysts for the reduction of CO2 to CH4. Unlike dense semiconductors, metal cations are successfully incorporated into the channels of the porous semiconducting materials to further tune the physical properties of the materials such as electrical conductivity and band gaps.