From Hydrogen Bond to van der Waals Force: Molecular Scalpel Strategy to Exfoliate a Two-Dimensional Metal-Organic Nanosheet.

The facile exfoliation of a two-dimensional metal-organic nanosheet of {[Co(HL)(H2O)(Py)3/4]·1/2H2O·DMF}n [1-Py; H3L = 5-(1H-pyrazol-4-yl)isophthalic acid and Py = pyridine] was achieved, via a molecular scalpel strategy, by weakening intermolecular forces between adjacent layers. The resulting 1-Py/KB40 (KB = Ketjen black) shows an increased oxygen evolution reaction (OER) performance with an overpotential of 370 mV at a current density of 10 mA cm-2 and a Tafel slope of 58 mV dec-1. This work sheds light on the structure-morphology-reactivity relationship of such materials in OER.

Regulation of Chirality in Metal-Organic Frameworks (MOFs) Based on Achiral Precursors through Substituent Modification.

The generation and regulation of chirality are closely related to the origin of life. Using achiral precursors to spontaneously build chiral MOFs remains a major challenge. Here, a method to synthesize chiral MOFs from achiral precursors by utilizing chiral fragments was achieved. The transformation from chiral fragments of 1 to chiral frameworks of 2 and 3 was realized by modifying the substituents, and the enantiomer resolution of 3-P41212 and 3-P43212 was achieved by d/l camphoric acid. 3 was then further studied in applications.

Response to the Temperature and Solvent Stimulation of MOF Material in a Single-Crystal to Single-Crystal Manner.

Under solvothermal conditions, a three-dimensional mononuclear crystal AQNU-1, {[Co(H2L)(DPD)(H2O)2]·2DMA}n (H2L = 5-(bis(4-carboxybenzyl)amino)isophthalic acid, DPD = 4,4'-(2,5-diethoxy-1,4-phenylene)dipyridine) has been synthesized. The transformations of AQNU-1 to binuclear {[Co2(L)(DPD)1.5(H2O)3]·DMA·H2O}n (AQNU-2) and pentanuclear {[Co5(L)2(DPD)2(OH)2]·2H2O}n (AQNU-3) were realized by double stimulation of temperature and solvent, which were accomplished by single-crystal to single-crystal (SC-SC) reaction.

A Europium-based MOF Fluorescent Probe for Efficiently Detecting Malachite Green and Uric Acid.

Lanthanide (such as Tb and Eu) metal-organic frameworks (MOFs) have been widely used in fluorescent probes because of their multiple coordination modes and brilliant fluorescence characteristic. Many lanthanide MOFs were applied in detecting metal ions, inorganic anions, and small molecules. However, it's rarely reported that Ln-MOF was devoted to detecting malachite green (MG) and uric acid (UA). We prepared a europium-based metal-organic framework (Eu-TDA) (TDA = 2,5-thiophenedicarboxylic acid group). Luminescence studies demonstrated that Eu-TDA can rapidly detect MG and UA with excellent selectivity and sensitivity, where individual quenching efficiency Ksv (MG: 5.8 × 105 M-1; UA: 4.15 × 104 M-1) and detection limit (MG: 0.0221 µM; UA: 0.689 µM) were regarded as the excellent MOF sensors for detecting MG and UA. The quenching of Eu-TDA's fluorescence emission by MG and UA was likely due to the spectral overlap, energy transfer, and competition. Among 11 metal cations and 14 anions, Eu-TDA can quickly and effectively recognize MG and UA with highly selective and sensitive properties. Our method possesses potential application in detecting UA in human blood and MG in the fishpond.

A Highly Solvent-Stable Metal-Organic Framework Nanosheet: Morphology Control, Exfoliation, and Luminescent Property.

Compared to bulk metal-organic framework (MOF), 2D MOF nanosheets have gained intensive research attention due to their ultrathin thickness and large surface area with highly accessible active sites. However, structural deterioration and morphological damage have impeded producing high-quality MOF nanosheets during exfoliation. Here, first a new layered bulk MOF ZSB-1 is synthesized and several solvents such as isopropanol, methanol, n-hexyl alcohol, and N,N-dimethylformamide are surveyed to examine their performance for the exfoliation of layered ZSB-1. As a result, a highly solvent-stable metal-organic framework rectangular nanosheet retaining undamaged morphology is obtained by the soft-physical method in n-hexyl alcohol. Theoretical simulations reveal that the strong interaction energy between n-hexyl alcohol and MOF layers is responsible for the best exfoliation performance of making the bulk MOF into nanosheets. In addition, ZSB-1 shows a tunable fluorescence peak position, fluorescent lifetime, and quantum yield by simply changing the solvent and morphology. Besides, the ZSB-1 was selected as a fluorescence sensor to detect metal ions, and ZSB-1 nanosheet exhibits excellent sensing ability for Fe3+ . It is worth noting that the ZSB-1 nanosheet has better detection limit performance of 0.054 × 10-6 m than that of its bulk counterpart.

Three Cd(II) MOFs with Different Functional Groups: Selective CO2 Capture and Metal Ions Detection.

Three Cd(II) iso-frameworks {[Cd(BIPA)(IPA)]·DMF} n (1), {[Cd(BIPA)(HIPA)]·DMF} n (2), and {[Cd(BIPA)(NIPA)]·2H2O} n (3) were synthesized from the self-assembly of the BIPA ligand (BIPA = bis(4-(1 H-imidazol-1-yl)phenyl)amine) and different carboxylic ligands (H2IPA = isophthalic acid, H2HIPA = 5-hydroxyisophthalic acid, H2NIPA = 5-nitroisophthalic acid) with Cd(II), which have amino groups, amino and phenolic hydroxyl groups, and amino and nitro groups, respectively. Both 1 and 2 exhibit CO2 uptakes of more than 20 wt %, indicating that amino and phenolic hydroxyl functionalized groups are beneficial to CO2 adsorption. Their applications and mechanisms in detecting metal ions were researched. The results exhibit that 1 and 2 are dual-responsive photoluminescent sensors for Hg2+ and Pb2+ ions with low detection concentration and high quenching constant. Besides, like most MOFs, 3 can detect a trace quantity of Fe3+ and Cu2+.

Exploring the Detection of Metal Ions by Tailoring the Coordination Mode of V-Shaped Thienylpyridyl Ligand in Three MOFs.

By employing a rational design approach, we synthesized three luminescent metal-organic frameworks (MOFs) 1-3 affording different coordination modes of V-shaped thienylpyridyl ligand. Their application in detecting metal ions was explored, and the mechanism was inferred. And the result exhibits that MOF 3 is a dual-responsive luminescent probe for Fe3+ and Al3+ ions.

H-Bonding Interactions Induced Two Isostructural Cd(II) Metal-Organic Frameworks Showing Different Selective Detection of Nitroaromatic Explosives.

Two luminescent Cd(II) metal-organic frameworks (MOFs) were prepared from electron-rich π-conjugated fluorescent ligands. They are isostructural with sql nets. Their strong luminescences can be quenched by a series of nitroaromatic explosives. Notably, MOF 1 shows highly selective and sensitive detection of 4-nitrophenol (4-NP), while MOF 2 exhibits good responses toward picric acid (PA) compared with other nitroaromatic explosives. This different order of quenching efficiency is because there are H-bonding interactions between MOF 1 and 4-NP, while MOF 2 lacks these H-bonding interactions. MOF 1 displays highly selective and sensitive detection of 4-NP with the high quenching constant (6.74× 104 M-1) and low detection limit (34.48 ppb), which is better than those of known MOFs. MOF 1 and MOF 2 have highly sensitive and selective detection of 4-NP and PA in the practical application, respectively.

Three Highly Stable Cobalt MOFs Based on "Y"-Shaped Carboxylic Acid: Synthesis and Absorption of Anionic Dyes.

Three Co(II) metal-organic frameworks (MOFs) were synthesized employing a rational design approach. On the basis of the different structures of three complexes, we tested their absorption properties toward two anionic dyes. The absorption results indicate that not only uncoordinated functional groups in the structure play an important role in adsorbing capacity but also physical forces can affect absorbing ability. Water stability testing shows that three crystals display high stability in aqueous solutions with different pH values. To our delight, the framework integrity of three complexes can be well-retained even after absorbing dyes.

D-D-π-A organic dyes containing 4,4'-di(2-thienyl)triphenylamine moiety for efficient dye-sensitized solar cells.

Dye-sensitized solar cells (DSSCs) are currently under intense academic and industrial investigations, because of their environmentally-friendly, efficient, and low-cost features. The photosensitizer plays a key role in determining DSSCs' performance. The 4,4'-di(2-thienyl)triphenylamine moiety, included in dye TTC102, has been demonstrated before as a novel and efficient electron donor fragment. In this paper, the oversimple π-conjugated bridge of TTC102 was replaced by a 9-ethyl-3,6-di(2-thiophenyl)carbazole moiety. Two new D-D-π-A sensitizers, named TTC104 and TTC105, were synthesized and fully characterized. After anchoring on TiO(2) nanoparticle film, the absorption band of TTC104 is broader by 30 nm than that of TTC102. Under AM 1.5G irradiation, the energy conversion efficiency (η) of a DSSC based on TTC104 reaches 6.36%, which is 21.6% higher than that of TTC102 (5.24%). The results above demonstrate that the photovoltaic performance can be improved after introducing the 9-ethyl-3,6-di(2-thiophenyl)carbazole moiety to TTC102 when employed in DSSCs. Dye TTC105, containing a pyridyl group as the electron acceptor, showed only 1.88% conversion efficiency (η) when used in DSSCs. The huge different performances of TTC104 and TTC105 are proved to be partly due to the smaller dye loading amount, higher dark current and charge recombination rate of TTC105.

The effect of optical properties on photovoltaic performance in dye-sensitized TiO2 nanocrystalline solar cells.

In this study, well-crystallized TiO2 nanoparticles with average size of -20 nm were synthesized by hydrolysis of titania salt in aqueous medium. The effect of the optical properties of the obtained titania particles based thin films with different thickness on the photovoltaic performance of dye-sensitized solar cells were investigated. Differential thermal analysis/thermo-gravimetric analysis, scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the morphology, structure and crystal formation of the obtained samples. The optical properties such as reflectance and transmittance of the photoanodes with different thickness were systematically investigated. The reflectance property increased with increasing the film thickness, however, the transmittance property showed the opposite way. The improved scattering property with increasing the film thickness facilitated efficient utilization of solar spectrum, which was verified by incident photon-to-current conversion efficiency. The maximum energy conversion efficiency of 5.0% was achieved on photoelectrode film with 17.8 microm.

Metal-organic frameworks constructed from versatile [WS4Cu(x)](x-2) units: micropores in highly interpenetrated systems.

Five metal-organic frameworks (MOFs) formed by [WS(4)Cu(x)](x-2) secondary building units (SBUs) and multi-pyridyl ligands are presented. The [WS(4)Cu(x)](x-2) SBUs function as network vertexes showing various geometries and connectivities. Compound 1 contains one-dimensional channels formed in fourfold interpenetrating diamondoid networks with a hexanuclear [WS(4)Cu(5)](3+) unit as SBU, which shows square-pyramidal geometry and acts as a tetrahedral node. Compound 2 contains brick-wall-like layer also with a hexanuclear [WS(4)Cu(5)](3+) unit as SBU. The [WS(4)Cu(5)](3+) unit in 2 is a new type of [WS(4)Cu(x)](x-2) cluster unit in which the five Cu(+) ions are in one plane with the W atom, forming a planar unit. Compound 3 shows a nanotubular structure with a pentanuclear [WS(4)Cu(4)](2+) unit as SBU, which is saddle-shaped and acts as a tetrahedral node. Compound 4 contains large cages formed between two interpenetrated (10,3)-a networks also with a pentanuclear [WS(4)Cu(4)](2+) unit acting as a triangular node. The [WS(4)Cu(4)](2+) unit in 4 is isomeric to that in 3 and first observed in a MOF. Compound 5 contains zigzag chains with a tetrahedral [WS(4)Cu(3)](+) unit as SBU, which acts as a V-shaped connector. The influence of synthesis conditions including temperature, ligand, anions of Cu(I) salts, and the ratio of [NH(4)](2)WS(4) to Cu(I) salt on the formation of these [WS(4)Cu(x)](x-2)-based MOFs were also studied. Porous MOF 3 is stable upon removal and exchange of the solvent guests, and when accommodating different solvent molecules, it exhibits specific colors depending on the polarity of incorporated solvent, that is, it shows a rare solvatochromic effect and has interesting prospects in sensing applications.

Improvement of dye-sensitized solar cells' performance through introducing suitable heterocyclic groups to triarylamine dyes.

Dye-sensitized solar cells are currently under intense academic and industrial investigation, owing to their great potential to serve as a low-cost alternative to existing photovoltaic technologies. This paper puts forward a method, which adopts heterocyclic substituted triarylamine units as electronic donor moieties, to design triarylamine dyes for efficient dye-sensitized solar cells. Three novel triarylamine dyes named TTC101, TTC102 and TTC103, were synthesized economically through modification of the structure of a simple triarylamine dye (TC105) using three kinds of heterocyclic groups (4-pyridyl, 2-thienyl and 1-pyrazolyl). The crystal structure of TTC103 indicates that the heterocyclic groups would partly delocalize the positive charge after photooxidation. The overall solar-to-electrical energy conversion efficiencies (η) of TTC102 and TTC103 are 4.92% and 5.21% respectively under AM1.5G irradiation, reaching ∼82.3% and ∼77.7% of a N719-based reference cell under the same conditions. Besides, the energy conversion efficiencies (η) of TTC102 and TTC103 are 1.29 and 1.37 times the efficiency of TC105 respectively. All of the results above demonstrate that photovoltaic performance can be improved by introducing suitable heterocyclic groups to triarylamine dyes. A series of properties were investigated to explain the results, with a special emphasis on the geometric structures, energetics, and charge transfer processes at the dye/titania/electrolyte interface.

Solvatochromic behavior of a nanotubular metal-organic framework for sensing small molecules.

A nanotubular metal-organic framework (MOF), {[(WS(4)Cu(4))I(2)(dptz)(3)]·DMF}(n) (dptz = 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, DMF = N,N-dimethylformamide) for sensing small solvent molecules is presented. When accommodating different solvent molecules as guests, the resulting inclusion compounds exhibit different colors depending on the solvent guests, and more interestingly, the band gaps of these solvent-included complexes are in linear correlation with the polarity of the guest solvents. The solvent molecules can be sensed by the changes of UV-vis spectra of the corresponding inclusion compounds, showing a new way of signal transduction as a new kind of sensor. The sensing by such a MOF occurs within the channel-containing material rather than on the external surface.

The difference in the CO2 adsorption capacities of different functionalized pillar-layered metal-organic frameworks (MOFs).

The excessive use of fossil energy has caused the CO2 concentration in the atmosphere to increase year by year. MOFs are ideal CO2 adsorbents that can be used in CO2 capture due to their excellent characteristics. Studies of the structure-activity relationship between the small structural differences in MOFs and the CO2 adsorption capacities are helpful for the development of efficient MOF-based CO2 adsorbents. Therefore, a series of pillar-layered MOFs with similar structural and different functional groups were designed and synthesized. The CO2 adsorption tests were carried out at 273 K to explore the relationship between the small structural differences in MOFs caused by different functional groups and the CO2 adsorption capacities. Significantly, compound 6 which contains a pyridazinyl group has a 30.9% increase in CO2 adsorption capacity compared to compound 1 with no functionalized group.

Molecular engineering in a family of pillared-layered metal-organic frameworks for tuning gas adsorption behavior.

In this work, inspired by a water-assisted three-dimensional supramolecular structure 1, we use a mixed-ligand strategy to form a 3D pillared-layered matrix by the introduction of linear ligands to compete against the water molecules. The resulting analogue microporous MOFs of 2-H, 2-F and 2-N, decorated with different functional groups, similarly show the CO2 uptake. Thanks to the negligible N2 adsorption capacity, enhanced selective adsorption towards CO2 is achieved in compound 2-N. That is, we present here an alternative plan for the high CO2 selective adsorption performance. In addition, the structure stability and moderate affinity for CO2 of these microporous MOFs endow them with excellent reusability.

Mixed matrix membranes containing fluorescent coordination polymers for detecting Cr2O72- with high sensitivity, stability and recyclability.

Three coordination polymers (CPs) were synthesized by using CdII, fluorescent 9,10-di(4-pyridyl)anthracene (dpa), and cyclohexane-1,4-dicarboxylic acid (H2cda), and they are [Cd2(dpa)2(cda)Cl2]n (1), [Cd(dpa)2(cda)]n (2) and [Cd(dpa)(cda)(H2O)]n (3). Both 1 and 2 are fluorescent and contain nonporous layers. 3 is an isomer of 2 and contains a porous diamondoid network. Fluorescent mixed matrix membranes were prepared by dispersing the particles of 1 or 2 within the matrix of polymethyl methacrylate, and showed high sensitivity and selectivity for detecting Cr2O72- in water. Both stability and recyclability of the MMMs were remarkably higher than those of the CP powders.

Three metal-organic framework isomers of different pore sizes for selective CO2 adsorption and isomerization studies.

Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) with tunable pore sizes, shapes and functionalities have excellent prospects in many applications, such as carbon capture. Molecular sieving can usually enable very high CO2 adsorption selectivity but has rarely been achieved, because it is difficult to precisely control the pore size in the range of 3-4 Å. We report here three MOF isomers built from CdII, terephthalic acid and 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine with the same stoichiometric ratio, among which 1 and 2 are framework-catenation isomers and 2 and 3 are framework-topological isomers. 1 contains 2-fold interpenetrated networks (topology of pcu) and 1D ultra-micropores and shows highly selective adsorption of CO2 over N2 and CH4, which is mainly ascribed to the molecular sieving effect of the framework. 2 contains a pcu network with 3D interconnected micropores, and 3 contains a kag network with much larger pores of 15 Å. Framework isomerization, in this case, was shown to be a feasible way of tuning the pore size of a MOF for selective CO2 adsorption. The effects of hydrothermal reaction conditions and additives on the structures and the formation of the MOF isomers were also studied.

Tetrazole-based porous metal-organic frameworks for selective CO2 adsorption and isomerization studies.

Tetrazole-based molecules have numerous bridging coordination modes which afford great synthetic possibilities for the preparation of porous metal-tetrazolate architectures for many applications, such as carbon capture. We reported here three tetrazole-based MOFs: 1, {[Cu12(ttz)8/3Cl5(H2O)16]11+·11Cl-}n (H3ttz = N2,N4,N6-tris(4-(1H-tetrazol-5-yl)phenyl)-1,3,5-triazine-2,4,6-triamine), contains highly positively charged Cu12 clusters and the largest mesopores (32 Å) among the reported MOFs based on a tri-topic tetrazole ligand. 2 and 3 are two MOF isomers built by using CuII and 2-(1H-tetrazol-5-yl)pyrimidine. 3 contains nonporous layers, while 2 contains 1D channels and showed high selectivity for adsorbing CO2, which should be attributed to the high density of free nucleophilic tetrazole N atoms on the pore surfaces. We found that the isomerization between 2 and 3 was caused by the diverse coordination modes of tetrazole-based ligands and can be controlled in synthesis processes.

An excellent example illustrating the fluorescence sensing property of cobalt-organic frameworks.

A novel luminescent cobalt-organic framework was assembled and employed as a chemosensor for the detection of metal ions via fluorescence enhancement and quenching. The sensing mechanism was based on the exposed pyridyl and carboxyl functional sites in the MOF structure, which interacted with metal ions via Lewis acid-base interactions and electrostatic interactions.