Topotactic Conversion of Titanium-Oxo Clusters to a Stable TOC-Based Metal-Organic Framework with the Selective Adsorption of Cationic Dyes.

Titanium-oxo cluster (TOC)-based metal-organic frameworks (MOFs) have received considerable attention in recent years due to their ability to expand the application of TOCs to fields that require highly stable frameworks. Herein, a new cyclic TOC formulated as [Ti6O6(OiPr)8(TTFTC)(phen)2]2 (1, where TTFTC = tetrathiafulvalene tetracarboxylate and phen = phenanthroline) was crystallographically characterized. TOC 1 takes a rectangular ring structure with two phen-modified Ti6 clusters as the width and two TTFTC ligands as the length. An intracluster ligand-to-ligand (TTF-to-phen) charge transfer in 1 was found for TOCs for the first time. Compound 1 undergoes topotactic conversion to generate stable TOC-MOF P1, in which the rectangular framework in 1 formed by a TOC core and ligands is retained, as verified by comprehensive characterization. P1 shows an efficient and rapid selective adsorption capacity for cationic dyes. The experimental adsorption capacity (qex) of P1 reaches a value of up to 789.2 mg/g at 298 K for the crystal violet dye, which is the highest among those of various adsorbents. The calculated models are first used to reveal the structure-property relationship of the cyclic host to different guest dyes. The results further confirmed the host MOF structure of P1.

A Cyclic Titanium-Oxo Cluster with a Tetrathiafulvalene Connector as a Precursor for Highly Efficient Adsorbent of Cationic Dyes.

Titanium-oxo clusters (TOCs) have been studied for applications in catalysis, energy storage and transfer, light emission, and so on; however, use of TOCs for the selective adsorption of dyes has not yet been reported. Herein, a TOC compound formulated as [Ti6O3(OiPr)14(TTFTC)]4 (1, TTFTC = tetrathiafulvalene-tetracarboxylate) was successfully prepared and crystallographically characterized. Compound 1 has a cyclic structure assembled by four Ti6 clusters and four rodlike TTFTC connectors. Red compound 1 self-condenses to form a black polymeric organic-inorganic hybrid material (denoted as B-1), which was characterized by various techniques. B-1 is an amorphous TiO material that is formed by the irregular condensation of 1 by the removal of alkoxyl groups. B-1 exhibits high dye adsorption efficiency toward cationic dyes with a qe value of 651.3 mg/g at 298 K for methylene blue (MB). Moreover, B-1 can be used to selectively remove MB not only from mixed cationic-anionic dye solutions but also from some mixed cationic dyes, which is related to their structures. Kinetic, isotherm, and thermodynamic studies demonstrated that the pseudo-second-order kinetic model and Freundlich model show a good fit to the experimental data. The adsorption process involves an exothermic and entropy decreasing process. In addition, dye-adsorbed B-1 can be further used as a photocurrent-responsive material. The work opens up a new field for the application of TOCs in the selective adsorption and removal of dyes.

Photocurrent and Gelation Properties of Polyphenol-Modified Titanium-Oxo Compounds.

Organic-inorganic hybrid metal-polyphenols as stable structural modules have gained extensive interest due to their diverse applications. However, titanium-oxo compounds (TOCs) with large molecular polyphenols have been less explored, and they were expected to be different from small polyphenols with isolated metal ions. Herein, 4-methyl-esculetin (Mesc), a catechol derivative, was selected to construct three TOCs, namely, [Ti17O24(Mesc)4(OiPr)16] (1), [Ti12O14(OiPr)18][Ti16O14(Mesc)12(OiPr)14] (2), and [Ti3O(Mesc)2(OAc)2(OiPr)4] (3). These compounds were structurally characterized. Photocurrent responses were evaluated using the compound-sensitized TiO2 electrodes. It was found that the current densities of 1-3 electrodes are in the order of 1 ≫ 3 > 2, which relates to the ligand-to-TiO core and ligand-to-ligand charge transfers (LMCT and LLCT, respectively). Density functional theory calculations showed that the lowest band gap of 1 originates from its LLCT. Compound 1 reacted with polyphenol tannin (TA) to form a fully transparent and robust gel (1-TA), and the gelation properties were investigated. Using the gel as a nano-TiO2 fixing agent, solar cell electrodes were prepared by a low-temperature wet method. The photocurrent responsive behavior of the 1-TA/TiO2 electrode was compared with that of the 1-sensitized traditional high-temperature-treated TiO2 electrode. Although the current density of the former is somewhat lower than that of the traditional electrode, the low-temperature wet preparation of the 1-TA/TiO2 electrode is more energy-efficient and sustainable.

An Octanuclear Cobalt Cluster Protected by Macrocyclic Ligand: In Situ Ligand-Transformation-Assisted Assembly and Single-Molecule Magnet Behavior.

Macrocyclic molecules with multiple coordination sites have been widely used as promising ligands to build polynuclear metal clusters; however, cyclic silsesquioxane-based metal clusters are still rare. Herein, we report a new octanuclear Co-silsesquioxane cluster [Co8(OH)2{(MeSiO2)6}2(bpy)2(Obpy)2] (SD/Co8c; SD = SunDi), wherein the Co8 disc-like core is sandwiched by two hexamethylcyclohexasiloxanolate ligands (MeSiO2)6 at two poles and finally encircled by two bpy (bpy = 2,2'-bipyridine) and two Obpy (HObpy = 6-hydroxy-2,2'-bipyridine) ligands at the equatorial region. Interestingly, both MeSi(OMe)3 and bpy undergo in situ transformations to generate hexameric cyclic (MeSiO2)6 and Obpy, respectively. The unusual hydroxylation of bpy and the OH- anion in the center of Co8 core provide additional binding sites to induce the formation of the larger cluster instead of the traditional hexanuclear cluster. The solution stability and fragmentation route in the gas phase were studied by cold-spray ionization and collision-induced dissociation mass spectrometry, respectively. Both results reveal that the Co8 core is quite stable in solution as well as in the gas phase, even with increased collision voltage. Magnetic susceptibility studies of SD/Co8c show the slow magnetization relaxation indicative of single-molecule magnet (SMM) behavior. This work not only presents the multiple in situ ligand-transformation-assisted assembly of polynuclear cobalt cluster but also provides some new insights into the magnetism-structure relationship for SMMs.

Effects of the Ligand Structures on the Photoelectric Activities, a Model Study Based on Titanium-Oxo Clusters Anchored with S-Heterocyclic Ligands.

Titanium oxo clusters (TOCs) have become one of the worldwide hot research topics because they are excellent molecular TiO materials having unique photoactive properties and can been used as models of dye-sensitized solar cells (DSSCs). S-Heterocyclic ligands such as thiophene (Th) and tetrathiafulvalene (TTF) derivatives have been widely used in electronic or photoelectronic devices and solar cells. However, a study of the synthesis and properties of TOCs anchored with Th and TTF derivatives is missing. Herein four such TOCs as single crystals were synthesized and structurally characterized: [Ti3O(OiPr)8(LTh)2] (1), [Ti4O2(OiPr)10(LTTF)2] (2), [Ti6O4(OiPr)10(LTh)2(O3PPh)2] (3), and [Ti6O4(OiPr)10(LTTF)2(O3PPh)2] (4). Charge transfer from the Th or TTF electron donor to the TOC core was evaluated by electronic spectra and theoretical calculations. This work first systematically investigated the photoelectrochemistry of TOCs with different conjugated S-heterocyclic ligands in molecular levels. The photocurrent densities of these cluster-modified TiO2 electrodes were examined using DSSCs, which were well responsive to irradiation. The photocurrents of TTF cluster-modified electrodes are higher than those of the Th cluster-modified electrodes because of the sulfur-rich conjugated system.

Fluorescent Hydrogel Generated Conveniently from a Perylene Tetracarboxylate Derivative of Titanium(IV) Alkoxide.

Organic gelators and metal-coordination frameworks based on perylene derivatives as functional materials have attracted great attention because of their intense fluorescence emission as well as unique electronic and photonic properties. We report here the structures and properties of a luminescent titanium(IV) coordination compound of a perylene tetracarboxylate (PTC) derivative, [Ti2(OiPr)6(L1)(phen)2] (1), along with its two naphthalene analogues, [Ti2(OiPr)6(L2)(phen)2] (2) and [Ti2(OiPr)6(L2)(bpy)2] (3), where L1 = 3,9-dicarboxylate-(4,10-diisopropanolcarboxylate)perylene, phen = 1,10-phenanthroline, L2 = 1,5-dicarboxylate-(2,6-diisopropanolcarboxylate)naphthalene, and bpy = 2,2'-bipyridine. Compound 1 is a rare early-transition-metal PTC coordination compound that can be simply prepared in one pot as crystals by a low-heat synthesis. Unlike those of paramagnetic late-transition-metal PTC compounds, compound 1 showed intense fluorescence emission. More remarkably, the crystals of 1 can be turned immediately to a fluorescent hydrogel just through a simple procedure, putting the crystals in water and then treating with ultrasound. No acid catalyst or pH adjustment is needed. Hydrolysis of the titanium isopropanol group in water and π-π interaction of the perylene and phen play important roles in the gelation process. The film prepared from the gel can be used as a visual fluorescence sensor for aromatic amines and phenols, which are hazards for the human and environment.

A Titanium Oxo Cluster Model Study of Synergistic Effect of Co-coordinated Dye Ligands on Photocurrent Responses.

The use of multiple sensitizers in dye sensitized solar cells has been attractive as a promising way to achieve highly efficient photovoltaic performance. However, except for the complementary absorption, synergistic effects among the dye components have not been well understood. Herein, using ferrocene-1-carboxylate (FcCO2) and catechol (Cat) as dye ligands, two titanium oxo clusters (TOCs), [Ti3O(OiPr)6(Cat)(FcCO2)2] (1) and [Ti7O4(OiPr)8(Cat)5(FcCO2)2] (2), were synthesized and structurally characterized. Another TOC, [Ti7O3(OiPr)12(Cat)4( o-BDC)] (3) ( o-BDC = o-benzene dicarboxylate), was also prepared as a contrast. Electronic spectra and theoretical calculations showed that charge transfer occurs from ligands FcCO2 and Cat to the TiO cluster core and the contribution of redox active FcCO2 is greater than that of Cat. Using the clusters as TiO-dye pre-anchored precursors, multi-dye sensitized TiO2 electrodes were prepared. Although the two dyes FcCO2 and Cat do not complement each other in spectra, a synergistic effect on the enhancement of photocurrent responses was found and discussed in view of the inter-dyes electron communication.

A Strong Donor-Acceptor System Based on a Metal Chalcogenide Cluster and Porphyrin.

Although great progress has been made for charge transfer (CT) compounds of various organic donor-acceptor systems, no CT compounds containing both inorganic chalcogenide cluster anions and organic porphyrin cations have been reported. Herein, a germanium chalcogenide cluster (Ge4S104-) is chosen as an electron donor and a methylated tetrakis(4-pyridyl)porphyrin (5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin, TMPyP) is selected as an electron acceptor to create chalcogenide cluster-porphyrin CT compounds (TMPyP-Ge4S10)·5H2O (1) and (MnTMPyP-Ge4S10)·13H2O (2). Their crystal structures have been characterized by single-crystal X-ray diffraction. Compound 1 is an ionic CT salt assembled through interion interactions, and compound 2 is a neutral CT dyad formed by metal-ligand axial coordination of the chalcogenide cluster with manganese porphyrin. The strong charge transfer properties are revealed by electronic spectra, theoretical calculations, 1H NMR, and ESR. The CT intensity of the chalcogenide cluster-porphyrin system can be modulated by metalation. The fluorescence and photocurrent response properties of 1 and 2 are related to the CT intensity.

Titanium Oxo Cluster with Six Peripheral Ferrocene Units and Its Photocurrent Response Properties for Saccharides.

A unique titanium oxo cluster with a ferrocene ligand was synthesized and characterized by single crystal X-ray analysis. Six ferrocene carboxylates coordinate to a D3d Ti6O6 core to be a redox active cluster 1, [Ti6O6(OiPr)6(O2CFc)6]. An analogue 2, [Ti6O6(OiPr)6(O2CiBu)6], where the redox active ferrocene group is replaced by isobutyrate, is also reported as a contrast. The six ferrocene moieties in 1 are structurally identical to give a main redox wave at E1/2 = 0.62 V in dichloromethane investigated by cyclic voltammetry. Photocurrent responses using electrodes of clusters 1 and 2 were studied, and the response properties of 1 are better than those of 2. The electronic spectra and theoretical calculations indicate that charge transfer occurs from ferrocene to Ti(IV) in 1, and the presence of the ferrocene moiety gives efficient electron excitation and charge separation. Cluster 1 is a cooperative system of TiO cluster and redox active ferrocene. Photocurrent response properties of an electrode of 1 for four saccharides, glucose, fructose, maltose, and sucrose, were tested, and only reducing sugars were responsive. The electrode of 2 is also photocurrent responsive to saccharides, but the current densities are lower than those of redox active 1.

Confinement Effects of Metal-Organic Framework on the Formation of Charge-Transfer Tetrathiafulvalene Dimers.

Three transition metal coordination polymers (CPs) based on the redox-active dimethylthio-tetrathiafulvalene-bicarboxylate (L) and 1,3-bi(4-pyridyl)propane (bpp) ligands, formulated as [MnL(bpp)]n (1), [CdL(bpp)]n (2), and [Cd2L(bpp)2(H2O)(C2O4)0.5]n·n(ClO4)·n(H2O) (3), are crystallographically characterized. Complexes 1 and 2 are isostructural 2-D polymers, and 3 features an unusual 3-D metal-organic framework (MOF). The 3-D MOF is constructed from tetranuclear cluster nodes built through the µ2-O bridge of the TTF ligand, which is first found for TTF coordination polymers. It is found that the channel generated by the 3-D MOF exerts a confinement effect on the formation of TTF dimers. The TTF dimers show strong intradimer interaction with partial electron transfer or charge transfer, and hence, the Cd compound 3 has relatively good photocurrent response property in comparison with that of 2-D Cd compound 2.

Ligand-to-Ligand Charge Transfer within Metal-Organic Frameworks Based on Manganese Coordination Polymers with Tetrathiafulvalene-Bicarboxylate and Bipyridine Ligands.

A systematic study on ligand-to-ligand charge-transfer (LLCT) properties of three closely related metal-organic frameworks (MOFs) is presented. These compounds are formulated as [MnL(4,4'-bpy)(H2O)]n·nCH3CN (1), [MnL(bpe)0.5(DMF)]n·2nH2O (2), and [MnL(bpa)(H2O)]n·2nH2O (3) (L = dimethylthio-tetrathiafulvalene-bicarboxylate, 4,4'-bpy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene, bpa = 1,2-bis(4-pyridyl)ethane). The X-ray single-crystal diffractions show that complexes 1-3 are all two-dimensional (2-D) coordination polymers with different frameworks in crystal lattices. Charge-transfer (CT) interactions within these MOFs are visually apparent in colors and vary according to the conjugated states of the bipyridine ligands (4,4'-bpy, bpe, and bpa). Theoretical calculations show that the charge transfer occurs from ligand L to bipyridine. The intensity of the LLCT is in the order of 2 > 1 > 3 investigated by theoretical calculations and ESR, which indicates that the intensity of CT is related to the bipyridyl conjugated state. Photocurrent responses of these compounds are consequently studied, and the results are in agreement with the intensity of charge transfer and linearly related to the LLCT energy.

An ionic charge-transfer dyad prepared cost-effectively from a tetrathiafulvalene carboxylate anion and a TMPyP cation.

Great progress has been made in combining a TTF moiety with a porphyrin unit by covalent bonds, but only a few examples were reported in which TTF and porphyrin assembled by noncovalent interactions. In contrast to the energy- and time-consuming synthetic procedures for the covalent system, the assembly of a non-covalent ionic system would be a cost-effective way to construct donor-acceptor ensembles. Herein a new type of ionic TTF-porphyrin dyad is obtained. A methylated tetra(4-pyridyl) porphyrin (5,10,15,20-tetrakis-(N-methyl-4-pyridyl)-porphyrin, TMPyP) is selected as the cation, and TTF-bicarboxylate (L(1)) or TTF-tetracarboxylate (L(2)) is used as the anion. Crystal structures of two TTF-TMPyP ionic D-A compounds, TMPyP-(HL(1))4·3H2O (1) and TMPyP-(H2L(2))2·5H2O (2), were characterized by single-crystal X-ray diffraction. The strong ionic interaction enhances the charge-transfer between the regular mixed-stacking donors and acceptors, which are investigated comprehensively by spectral, electrochemical and theoretical studies. The variation in properties between L(1) and L(2) is of great advantage to understand the influence factors for charge-transfer. The charge-transfer properties can be modulated not only by the nature of the donor or the acceptor, but also the cation-anion ratio in the salt, which shows great flexibility of the D-A ionic dyad in the design and preparation of new charge-transfer systems.

Copper-bipyridine grid frameworks incorporating redox-active tetrathiafulvalene: structures and supercapacitance.

Redox active tetrathiafulvalene (TTF) and its derivatives when used as electrode additives have exhibited improved energy efficiency and sustainability in batteries. However, the structure-property relationship has not been investigated in detail until very recently. In this work, three redox-active TTF compounds were synthesized, and formulated as [Cu(HL)2(bpa)2]n (1), [Cu(bpe)2(H2O)2]n·2n(HL)·nMeOH·nH2O (2), and [Cu(bpp)2(H2O)2]n·2n(HL) (3) (L = dimethylthio-tetrathiafulvalene-bicarboxylate) for this work. The effects of conjugated state and spacer length of the linkers on structural assembly and band gap as well as the interactions of TTF-TTF/TTF-bpy are discussed. Compound 1 is a bpa and HL co-coordinated 1D Cu(ii) polymer. Compounds 2 and 3 are 2D Cu(ii)-bipyridine (4,4) MOFs incorporating HL (1-) as free anion columns. The photocurrent density of 2 is larger than those of 1 and 3 due to a strong charge transfer from TTF to bpe in compound 2. The supercapacitance performances of these compounds were evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) techniques. The results revealed that the 2D MOF structures of 2 and 3 are beneficial for good specific capacitance values (Csp). This work revealed the structure-property relationships of TTF derivatives for use as electrode active materials in energy transfer and storage.

Tetrathiafulvalene-Based Metal-Organic Framework as a High-Performance Anode for Lithium-Ion Batteries.

Metal-organic frameworks (MOFs) have aroused great interest as lithium-ion battery (LIB) electrode materials. In this work, we first report that a pristine three-dimensional tetrathiafulvalene derivatives (TTFs)-based zinc MOF, formulated [Zn2(py-TTF-py)2(BDC)2]·2DMF·H2O (1) (py-TTF-py = 2,6-bis(4'-pyridyl)tetrathiafulvalene and H2BDC = terephthalic acid), can work as a high-performance electrode material for rechargeable LIBs. The TTFs-Zn-MOF 1 electrode displayed a high discharge specific capacity of 1117.4 mA h g-1 at a current density of 200 mA g-1 after 150 cycles along with good reversibility. After undergoing elevated discharging/charging rates, the electrode showed superior lithium storage performance in the extreme case of 20 A g-1 and could finally recover the capability when the current rate was back to 200 mA g-1. Particularly, specific capacities of 884.2, 513.8, and 327.8 mA h g-1 were reached at high current densities of 5, 10, and 20 A g-1 after 180, 175, and 300 cycles along with good reversibility, respectively. Such an excellent performance is first reported for the LIB anode materials. TTFs-Zn-MOF 2, namely, [Zn2(py-TTF-py) (BDC)2]·DMF·2H2O (2), was prepared as a contrast to explore the relationship between the structures of the electrode materials and the electrochemical properties. Based on the structural analysis of 1 and 2 and ex situ X-ray photoelectron spectroscopy, the TTF moiety and the twofold TTF pillar play a key role in the excellent electrochemical performance. The full cell of MOF 1 with NMC 622 delivered the capacity of 131.9 mA h g-1 at 100 mA g-1 with the Coulombic efficiency of 99.45% after 70 cycles and exhibited the tolerance to high-current operation.

The effects of transition-metal doping and chromophore anchoring on the photocurrent response of titanium-oxo-clusters.

Titanium-oxo-clusters (TOCs), [Ti6O4(OiPr)10(Cat)2(BA)2] (1) and [Ti12M2O10(OEt)22(Cat)2(BA)4] (M = Co, Mn, Ni, 2-4; H2Cat = catechol, HBA = benzoic acid) are prepared in one step in an in situ solvothermal synthesis. Cluster structures of 2-4 can be considered as two 1 moieties merged together by two transition metal atoms. Unlike most TOCs with sphere-like structures, clusters 2-4 feature a unique single layered structure. They are not only transition metal doped TOCs but also charge transfer (CT) TOCs, CT from Cat to the TiO cluster core. Photoelectrodes were prepared by dipping the solution of clusters on a porous TiO2 substrate. Photocurrent response properties of the electrodes were studied in comparison with those of the electrodes of non-metal doped 1 and the non-Cat coordinated Ti6 cluster. The results showed that the photocurrent densities of metal doped clusters are higher than that of non-doped clusters and the highest photocurrent density was found for the redox active Co(ii) doped cluster. Charge transfer also plays an effective role in photocurrent conversion under visible light irradiation.

Dye molecule bonded titanium alkoxide: a possible new type of dye for sensitized solar cells.

An organic dye coordinated titanium iso-propoxide compound is designed and synthesized. Taking advantage of the hydrolysis of the titanium alkoxide moiety on the surface of TiO2 electrode, the dye-semiconductor surface properties, including anchoring and dispersivity, are improved, which opens a new perspective to explore dyes for DSSCs.

A lanthanide-titanium (LnTi11) oxo-cluster, a potential molecule based fluorescent labelling agent and photocatalyst.

Although a lot of titanium oxo-clusters (TOCs) have been synthesized and characterized, research studies on their application properties are still limited. The work described here is not only aimed at the synthesis and crystal structures of the TOCs, but also aimed at exploration of their potential applications in molecule based fluorescence labelling and photocatalysis. Three heterometallic TOC compounds with lanthanide (Ln) elements Sm(iii) (1), Eu(iii) (2) and Gd(iii) (3) are prepared and their cluster structures are characterized as LnTi11 cages. Compound 2 exhibits the characteristic fluorescence of Eu(iii) and the emission intensity can be decreased upon irradiation and recovered by air oxidation, which is attributed to the energy transfer between Eu(iii) and photo-induced Ti(iii) of the oxo-TiO cluster. The fluorescence intensity of 2 can be significantly increased when treated with 1,10-phenanthroline. The catalytic properties of 2 were determined by the degradation of dyes on a paper substrate. Compound 2 has potential applications as a molecule based fluorescent labelling agent and photodegeneration catalyst.

Two Ti13-oxo-clusters showing non-compact structures, film electrode preparation and photocurrent properties.

Two benzene dicarboxylate (BDC) and salicylate (SAL) substituted titanium-oxo-clusters, Ti13O10(o-BDC)4(SAL)4(O(i)Pr)16 (1) and Ti13O10(o-BDC)4(SAL-Cl)4(O(i)Pr)16 (2), are prepared by one step in situ solvothermal synthesis. Single crystal analysis shows that the two Ti13 clusters take a paddle arrangement with an S4 symmetry. The non-compact (non-sphere) structure is stabilized by the coordination of BDC and SAL. Film photoelectrodes are prepared by the wet coating process using the solution of the clusters and the photocurrent response properties of the electrodes are studied. It is found that the photocurrent density and photoresponsiveness of the electrodes are related to the number of coating layers and the annealing temperature. Using ligand coordinated titanium-oxo-clusters as the molecular precursors of TiO2 anatase films is found to be effective due to their high solubility, appropriate stability in solution and hence the easy controllability.