Lei Zhang

Construction of molecular rectangles with titanium–oxo clusters and rigid aromatic carboxylate ligands

Co-reporter:Qing-Rong Ding;Jin-Xiu Liu;Nagaraju Narayanam;Jian Zhang

Dalton Transactions 2017 vol. 46(Issue 46) pp:16000-16003

Publication Date(Web):2017/11/28

DOI:10.1039/C7DT03470A

Four rectangular molecular architectures have been successfully constructed using {Ti5O7} clusters as inorganic vertical edges and bridging aromatic carboxylates as horizontal edges. The introduced organic ligands show a strong influence on the light absorption behaviors of the obtained hybrid complexes.

Improving the photocatalytic H2 evolution activities of TiO2 by modulating the stabilizing ligands of the nanoscale Ti8O8-cluster precursors

Co-reporter:Zongxiong Xu, Hao Fu, Tian Wen, Lei Zhang, Jian Zhang

International Journal of Hydrogen Energy 2017 Volume 42, Issue 39(Volume 42, Issue 39) pp:

Publication Date(Web):28 September 2017

DOI:10.1016/j.ijhydene.2017.08.083

•A cluster precursor-based methodology for TiO2 fabrication is established.•The thermolysis process towards TiO2 samples was affected by the cluster precursors.•The H2 production rates of TiO2 can be improved by selecting ligands on precursors.Titanium-oxo clusters (TOCs) are important model complexes and potential precise single-source precursors of TiO2 materials. We report here a series of TiO2 samples derived from TOCs with the same wheel-like Ti8O8 clustercore but different stabilizing ligands. Our results demonstrate that the ligands on TOCs not only influence the phase-transition during themolysis, but more importantly tune the photocatalytic H2 evolution activities of the obtained TiO2 materials. Through 500 °C calcination, the nanosized Ti8O8 cluster stabilized by organic benzoate ligands gives rise to a TiO2 sample with H2 production rate of 611 μmol/h/g. When the stabilizing ligands are changed to inorganic SO42−, a significant improvement of H2 evolution activity has been achieved, resulting in a 7-times higher value of 4527 μmol/h/g. This work provides a new strategy to produce TiO2 with enhanced and tunable photocatalytic activities from titanium-oxo cluster precursors.Download high-res image (445KB)Download full-size image

Synthesis and photocatalytic H2 evolution properties of four titanium-oxo-clusters based on a cyclohex-3-ene-1-carboxylate ligand

Co-reporter:Mei-Yan Gao;Shumei Chen;Lan-Xia Hu;Jian Zhang

Dalton Transactions 2017 vol. 46(Issue 32) pp:10630-10634

Publication Date(Web):2017/08/14

DOI:10.1039/C7DT00627F

Four titanium-oxo-clusters with cyclohex-3-ene-1-carboxylate (Cec) ligands, Ti6(μ2-O)2(μ3-O)2(Cec)4(OiPr)12 (PTC-91; HOiPr = isopropanol), Ti6(μ3-O)6(Cec)6(OiPr)6 (PTC-92 and PTC-93) and H2[Ti18(μ2-O)11(μ3-O)14(Cec)20(OiPr)4] (PTC-94), have been solvothermally synthesized under different conditions, respectively. These clusters with the same Cec ligand show totally different structures, and they are stable in water and other common solvents. The Ti6 clusters with different conformations are presented in PTC-91, PTC-92 and PTC-93, while PTC-94 is an unusual Ti18 cluster. The photocatalytic studies reveal that PTC-91 and PTC-94 have good H2 evolution ability.

Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by π-conjugated chromophores

Co-reporter:Nagaraju Narayanam;Wei-Hui Fang;Kalpana Chintakrinda;Jian Zhang

Chemical Communications 2017 vol. 53(Issue 57) pp:8078-8080

Publication Date(Web):2017/07/13

DOI:10.1039/C7CC04388K

Deep eutectic-solvothermal synthesis has been successfully employed to prepare four polyoxo-titanium clusters (PTCs), with nuclearity up to 28. The cluster cores obtained via this method are completely functionalized by conjugated ligands and display different photocatalytic H2 production activities.

Synthetic investigation, structural analysis and photocatalytic study of a carboxylate–phosphonate bridged Ti18-oxo cluster

Co-reporter:Wei-Hui Fang;Jian Zhang

Dalton Transactions 2017 vol. 46(Issue 3) pp:803-807

Publication Date(Web):2017/01/17

DOI:10.1039/C6DT04474C

By the combination of carboxylate and phosphonate ligands, we herein report a nanosized H2[Ti18(μ3-O)14(μ2-O)6(O3P-Phen)2(PA)16(OPri)14] (PTC-51) (HPA = propionic acid, O3P-Phen = phenyl phosphonate), whose structure can be observed as the linkage of independent phosphonate supporting and carboxylate bridging hexanuclear Ti(IV) clusters. We also demonstrate a concise crystalline phase diagram, which shows the important effect of phosphonate and carboxylate ligand ratio during synthetic reactions. The photocatalytic H2 evolution activities of the obtained polyoxotitanate materials have been studied, with carboxylate-Ti6 presenting the maximum H2 production rate up to 267.78 μmol g−1 h−1.

Cocrystal of {Ti4} and {Ti6} Clusters with Enhanced Photochemical Properties

Co-reporter:Jian-Fang Wang, Wei-Hui Fang, Dong-Sheng LiLei Zhang, Jian Zhang

Inorganic Chemistry 2017 Volume 56(Issue 5) pp:

Publication Date(Web):February 10, 2017

DOI:10.1021/acs.inorgchem.6b02913

Herein we report the construction of a supramolecular cocrystal {Ti4 + Ti6} through the combination of isolated {Ti4} and {Ti6} clusters. Moreover, the combined {Ti4 + Ti6} complex presents better solar-driven photocatalytic dye degradation activity than the individual {Ti4} and {Ti6} compounds.

Assembly of titanium-oxo cations with copper-halide anions to form supersalt-type cluster-based materials

Co-reporter:Wei-Hui Fang;Jian Zhang

Chemical Communications 2017 vol. 53(Issue 28) pp:3949-3951

Publication Date(Web):2017/04/04

DOI:10.1039/C7CC01443K

A series of binary cluster-based crystalline materials consisting of the same cationic polyoxotitanium cluster (PTC) and different anionic copper halide clusters (CuX) have been prepared. Interestingly, these complexes display analogous structure types to inorganic salts and present various light absorption properties.

p-Arsanilic acid stabilizing titanium-oxo clusters with various core structures and light absorption behaviours

Co-reporter:Bang-Chang Zhu, Lei Zhang, Jian Zhang

Inorganic Chemistry Communications 2017 Volume 86(Volume 86) pp:

Publication Date(Web):1 December 2017

DOI:10.1016/j.inoche.2017.09.015

•Arsonate ligands stabilizing titanium-oxo clusters have been firstly prepared.•The prepared clusters present different nuclearities and structures.•Bandgaps of the obtained complexes are highly dependent on their cluster cores and functionalizing ligands.A series of p-arsanilic acid stabilizing polyoxo‑titanium clusters (PTCs) have been successfully synthesized through solvothermal method, which present {Ti4}, {Ti5} and {Ti6} cores functionalized by different carboxylic acid ligands. PTC-111 displays a {Ti4} core structure which is stabilized by glycolic acid and esterified p-arsanilic acid. PTC-112, PTC-113 and PTC-114 have isostructural {Ti6} structures, functionalized by isonicotinic acid, 2-chloroisonicotinic acid and benzoic acid, respectively. The {Ti5} core of PTC-115 is functionalized by m-nitrobenzoic acid. It is interesting that the light absorption behaviours of these PTCs are dependent on their core structures and the functionalizing ligands.A series of p-arsanilic acid stabilizing polyoxo‑titanium clusters (PTCs) with {Ti4}, {Ti5} and {Ti6} cores have been synthesized and characterized, displaying different light absorption properties.Download high-res image (211KB)Download full-size image

A 3.6 nm Ti52–Oxo Nanocluster with Precise Atomic Structure

Co-reporter:Wei-Hui Fang; Lei Zhang;Jian Zhang

Journal of the American Chemical Society 2016 Volume 138(Issue 24) pp:7480-7483

Publication Date(Web):June 1, 2016

DOI:10.1021/jacs.6b03489

We report a 3.6 nm Ti52–oxo cluster with precise atomic structure, which presents a largest size record in the family of titanium–oxo clusters (TOCs). The crystal growth of such large Ti52 is based on a stepwise interlayer assembly approach from Ti6 substructures. The possible growth mechanism of Ti52 could be deduced from crystal structures of two substructures, Ti6 and Ti17, which were also synthesized under similar conditions as Ti52. Moreover, these TOCs show cluster-size-dependent photocatalytic hydrogen evolution activities with Ti52 giving a H2 production rate up to 398 μmol/h/g, which is also the highest record in the family of TOCs. This work not only represents a milestone in constructing large TOCs with comparable sizes as TiO2 nanoparticles but also brings significant advances in improving photocatalytic behaviors of TOCs.

Fullerene-like Polyoxotitanium Cage with High Solution Stability

Co-reporter:Mei-Yan Gao; Fei Wang; Zhi-Gang Gu; De-Xiang Zhang; Lei Zhang;Jian Zhang

Journal of the American Chemical Society 2016 Volume 138(Issue 8) pp:2556-2559

Publication Date(Web):February 19, 2016

DOI:10.1021/jacs.6b00613

We present the formation of the largest titanium–oxo cluster, [Ti42(μ3-O)60(OiPr)42(OH)12)]6–, with the first fullerene-like Ti–O shell structure. The {Ti42O60} core of this compound exemplifies the same icosahedral (Ih) symmetry as C60, the highest possible symmetry for molecules. According to the coordination environments, the Ti centers in this cluster can be arranged into a Platonic {Ti12} icosahedron and an Archimedean {Ti30} icosidodecahedron. The solution stability of this cluster was confirmed by electrospray ionization mass spectrometry. The spherical body of the {Ti42O60} core has an inside diameter of 1.05 nm and an outside diameter of 1.53 nm, which could be directly visualized by high-resolution transmission electron microscopy. Our results demonstrate that titanium oxide can also form fullerene-like shell structures.

Azole Functionalized Polyoxo-Titanium Clusters with Sunlight-Driven Dye Degradation Applications: Synthesis, Structure, and Photocatalytic Studies

Co-reporter:Nagaraju Narayanam, Kalpana Chintakrinda, Wei-Hui Fang, Yao Kang, Lei Zhang, and Jian Zhang

Inorganic Chemistry 2016 Volume 55(Issue 20) pp:10294-10301

Publication Date(Web):October 6, 2016

DOI:10.1021/acs.inorgchem.6b01551

Six polyoxo-titanium clusters (PTCs) with varying nuclearities containing Ti–N bonds and heteronuclearity, namely, [Ti6(μ3-O)2(μ2-O)2(O3P-Phen)2(OiPr)10(1-hbta)2] (PTC-37), Ti8(μ3-O)2(μ2-O)2(O3P-Phen)2(OiPr)16(adn)2(NO3)2] (PTC-38), [Ti4(μ3-O)(μ2-O)(μ2-OiPr)2(OiPr)4(O3P-Phen)3(1,10-phn)](HOiPr) (PTC-39), [Ti4(μ3-O)(μ2-OiPr)3(OiPr)5(O3P-Phen)3(Im)] (PTC-40), [Ti4(μ3-O)(μ2-OiPr)3(OiPr)5(O3P-Phen)3(Im)][Ti3M(μ3-O)(μ2-OiPr)3(OiPr)3(O3P-Phen)3(Im)] (M = Co for PTC-41 and M = Zn for PTC-42; O3P-Phen = phenyl phosphonate, 1-hbta = 1-hydroxy benzotriazolate, adn = adenine, 1,10-phn = 1,10-phenanthroline, Im = imidazolate, and OiPr = isopropoxide) were prepared as crystalline samples and structurally characterized. Simultaneous doping of nitrogen and transition metal heteroatoms into the Ti–O clusters created complex chemical environments in the resulting hybrid materials. Thus, photocatalytic methylene blue degradation studies were performed to understand structure–property relationships in these Ti cluster-based materials. The complex chemical environment created in these novel molecular clusters had proved to exhibit ligand-dependent photocatalytic activities under normal sunlight. Adenine-functionalized PTC-38 presented moderate activities, while other PTCs all show rapid dye degradation.

A new cadmium-doped titanium–oxo cluster with stable photocatalytic H2 evolution properties

Co-reporter:Jin-Xiu Liu, Xian-Chong Zeng, Lei Zhang and Jian Zhang

Dalton Transactions 2016 vol. 45(Issue 11) pp:4501-4503

Publication Date(Web):12 Feb 2016

DOI:10.1039/C6DT00333H

A new Cd-doped titanium–oxo cluster (TOC) stabilized by tert-butylacetic acid ligands has been prepared through an easily handled solvothermal reaction; photocatalytic studies indicate that it displays good H2 evolution ability (3.15 μmol h−1), and moreover preserves high catalytic stability.

Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal–Organic Nanoclusters into Molecular Framework Pores

Co-reporter:Zhi-Gang Gu, Hao Fu, Tobias Neumann, Zong-Xiong Xu, Wen-Qiang Fu, Wolfgang Wenzel, Lei Zhang, Jian Zhang, and Christof Wöll

ACS Nano 2016 Volume 10(Issue 1) pp:977

Publication Date(Web):December 7, 2015

DOI:10.1021/acsnano.5b06230

We describe the fabrication of hybrid yet well-ordered porous nanoparticle (NP) arrays with full three-dimensional periodicity by embedding nanometer-sized metal–organic clusters (MOCs) into metal–organic frameworks (MOFs). Although conventional NP@MOF encapsulation procedures failed for these fairly large (1.66 nm diameter) NPs, we achieved maximum loading efficiency (one NP per pore) by using a modified liquid phase epitaxy (LPE) layer-by-layer approach to grow and load the MOF. The preformed NPs, homochiral Ti4(OH)4(R/S-BINOL)6 clusters (Ti-MOC, BINOL = 1,1′-bi-2-naphthol), formed a regular lattice inside the pores of an achiral HKUST-1 (or Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) MOF thin film. Exposure to the different enantiomers of methyl lactate revealed that the NP@MOF metacrystal is quite efficient regarding enantiomer recognition and separation. The approach presented here is also suited for other MOF types and expected to provide a substantial stimulus for the fabrication of metacrystals, crystalline solids made from nanoparticles instead of atoms.Keywords: homochirality; metacrystals; metal−organic framework; nanocluster;

Bandgap Engineering of TitaniumOxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation

Co-reporter:Jin-Xiu Liu;Mei-Yan Gao;Dr. Wei-Hui Fang;Dr. Lei Zhang;Dr. Jian Zhang

Angewandte Chemie International Edition 2016 Volume 55( Issue 17) pp:5160-5165

Publication Date(Web):

DOI:10.1002/anie.201510455

Abstract

Through the labile coordination sites of a robust phosphonate-stabilized titanium–oxo cluster, 14 O-donor ligands have been successfully introduced without changing the cluster core. The increasing electron-withdrawing effect of the organic species allows the gradual reduction of the bandgaps of the {Ti₆} complexes. Transition-metal ions are then incorporated by the use of bifunctional O/N-donor ligands, organizing these {Ti₆} clusters into polymeric structures. The coordination environments of the applied metal ions show significant influence on their visible-light adsorption. Both the above structural functionalizations also tune the photocatalytic H₂ production activities of these clusters. This work provides a systematic bandgap engineering study of titanium–oxo clusters, which is important not only for their future photocatalytic applications, also for the better understanding of the structure–property relationships.

Frontispiece: Bandgap Engineering of TitaniumOxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation

Co-reporter:Jin-Xiu Liu;Mei-Yan Gao;Dr. Wei-Hui Fang;Dr. Lei Zhang;Dr. Jian Zhang

Angewandte Chemie International Edition 2016 Volume 55( Issue 17) pp:

Publication Date(Web):

DOI:10.1002/anie.201681761

Bandgap Engineering of TitaniumOxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation

Co-reporter:Jin-Xiu Liu;Mei-Yan Gao;Dr. Wei-Hui Fang;Dr. Lei Zhang;Dr. Jian Zhang

Angewandte Chemie 2016 Volume 128( Issue 17) pp:5246-5251

Publication Date(Web):

DOI:10.1002/ange.201510455

Abstract

Through the labile coordination sites of a robust phosphonate-stabilized titanium–oxo cluster, 14 O-donor ligands have been successfully introduced without changing the cluster core. The increasing electron-withdrawing effect of the organic species allows the gradual reduction of the bandgaps of the {Ti₆} complexes. Transition-metal ions are then incorporated by the use of bifunctional O/N-donor ligands, organizing these {Ti₆} clusters into polymeric structures. The coordination environments of the applied metal ions show significant influence on their visible-light adsorption. Both the above structural functionalizations also tune the photocatalytic H₂ production activities of these clusters. This work provides a systematic bandgap engineering study of titanium–oxo clusters, which is important not only for their future photocatalytic applications, also for the better understanding of the structure–property relationships.

Frontispiz: Bandgap Engineering of TitaniumOxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation

Co-reporter:Jin-Xiu Liu;Mei-Yan Gao;Dr. Wei-Hui Fang;Dr. Lei Zhang;Dr. Jian Zhang

Angewandte Chemie 2016 Volume 128( Issue 17) pp:

Publication Date(Web):

DOI:10.1002/ange.201681761

A structure-directing method to prepare semiconductive zeolitic cluster–organic frameworks with Cu3I4 building units

Co-reporter:Yao Kang, Wei-Hui Fang, Lei Zhang and Jian Zhang

Chemical Communications 2015 vol. 51(Issue 43) pp:8994-8997

Publication Date(Web):21 Apr 2015

DOI:10.1039/C5CC02598B

Two semiconductive cluster–organic frameworks based on Cu4I4 and Cu3I4 building units were obtained by the use of different organic structure-directing agents; the latter Cu3I4 nodes are tetrahedrally connected through 1,4-diazabicyclo[2.2.2]octane (DABCO) linkers and Cu–I bridges, giving rise to a zeolitic framework with SOD topology.

Multiarylpolycarboxylate-Mediated Hybrid Cobalt Phosphate Frameworks with Supramolecular Zeolitic Topology and Unusual I2O2 Connectivity

Co-reporter:Qing-Rong Ding, Li-Ming Li, Lei Zhang, and Jian Zhang

Inorganic Chemistry 2015 Volume 54(Issue 4) pp:1209-1211

Publication Date(Web):January 23, 2015

DOI:10.1021/ic502895u

Two novel organic–inorganic hybrid frameworks containing multiarylpolycarboxylate linkers and cobalt phosphate layers, [H2DABCO]·[Co(HPO4)(bpdc)] (1) and [H2DABCO]3·[Co10(npa)3(PO4)6Cl2] (2), where bpdc = 4,4′-biphenyldicarboxylate, npa = 2,6-naphthalenedicarboxylate, and DABCO = 1,4-diazabicyclo[2.2.2]octane, have been solvothermally synthesized. Compound 1 features a 3D zeolite-like supramolecular network with ABW topology, and compound 2 is a 3D framework structure with unusual I2O2 connectivity.

A Series of Homochiral Helical Metal–Organic Frameworks Based on Proline Derivatives

Co-reporter:Zhong-Xuan Xu, Yu-Lu Ma, Yu Xiao, Lei Zhang, and Jian Zhang

Crystal Growth & Design 2015 Volume 15(Issue 12) pp:5901

Publication Date(Web):November 5, 2015

DOI:10.1021/acs.cgd.5b01359

Eight novel three-dimensional homochiral helical metal–organic frameworks (HHMOFs), namely, [Cd3((S)-PIA)2(PPA)(H2O)2]n (1-L), [Cd3((R)-PIA)2(PPA)(H2O)2]n (1-D), [Cd4((R)-PIA)3(DPP)4(H2O)4]n (2-D), [Cd1.5((S)-PIA)(4,4′-DIB)2]n (3-L), [Cd1.5((S)-PIA)(DPEE)1.5]n (4-L), [Cd1.5((R)-PIA)(DPEE)1.5]n (4-D), [Cd1.5((S)-PIA)(DPEA)1.5]n (5-L), and [Cd1.5((S)-PIA)(DPEA)1.5]n (5-D) (H3PIA = 5-(2-carboxypyrrolidine-1-carbonyl) isophthalic acid) have been synthesized using proline-derived ligands ((S)-H3PIA and (R)-H3PIA). Crystallographic analysis indicates that all the complexes contain homochiral left- and/or right-handed helical chains, which are constructed by PIA fragments and Cd(II) ions. Meanwhile, in these complexes nitrogen heterocycle auxiliary ligands play an important role in structural diversity. Some physical characteristics, such as thermal stabilities, solid-state circular dichroism, and photoluminescent properties, are also investigated. Our results highlight an effective method to apply proline ligands to construct interesting HHMOFs.

Homochiral Cluster-Organic Frameworks Constructed from Enantiopure Lactate Derivatives

Co-reporter:Zhong-Xuan Xu, Yu Xiao, Yao Kang, Lei Zhang, and Jian Zhang

Crystal Growth & Design 2015 Volume 15(Issue 9) pp:4676

Publication Date(Web):August 10, 2015

DOI:10.1021/acs.cgd.5b00958

Two enantiopure organic linkers ((R)-H3CIA and (S)-H3CIA) derived from lactic acid have been synthesized and used to construct four pairs of homochiral metal–organic frameworks (HMOFs) with polymetallic building blocks. Crystallographic analysis indicates that H3CIA ligands can connect tetranuclear zinc units into kgd type layered structure, while the introduction of nitrogen heterocycle auxiliary ligands into this system gives rise to the formation of three-dimensional homochiral MOFs with different structural topologies. Physical characteristics of these complexes are also carried out, including thermal stabilities, solid-state circular dichroism (CD), and photoluminescent properties. Our results highlight the effective method to apply inexpensive and nontoxic chiral ligands to prepare interesting HMOFs.

Two luminescent bcu-type metal-organic frameworks constructed from distinct cadmium clusters

Co-reporter:Ye-Yan Qin, Qing-Rong Ding, E Yang, Yao Kang, Lei Zhang, Yuan-Gen Yao

Inorganic Chemistry Communications 2015 Volume 56() pp:83-86

Publication Date(Web):June 2015

DOI:10.1016/j.inoche.2015.03.054

Assembly of titanium-oxo cations with copper-halide anions to form supersalt-type cluster-based materials

Co-reporter:Wei-Hui Fang, Lei Zhang and Jian Zhang

Chemical Communications 2017 - vol. 53(Issue 28) pp:NaN3951-3951

Publication Date(Web):2017/03/13

DOI:10.1039/C7CC01443K

A series of binary cluster-based crystalline materials consisting of the same cationic polyoxotitanium cluster (PTC) and different anionic copper halide clusters (CuX) have been prepared. Interestingly, these complexes display analogous structure types to inorganic salts and present various light absorption properties.

A new cadmium-doped titanium–oxo cluster with stable photocatalytic H2 evolution properties

Co-reporter:Jin-Xiu Liu, Xian-Chong Zeng, Lei Zhang and Jian Zhang

Dalton Transactions 2016 - vol. 45(Issue 11) pp:NaN4503-4503

Publication Date(Web):2016/02/12

DOI:10.1039/C6DT00333H

A new Cd-doped titanium–oxo cluster (TOC) stabilized by tert-butylacetic acid ligands has been prepared through an easily handled solvothermal reaction; photocatalytic studies indicate that it displays good H2 evolution ability (3.15 μmol h−1), and moreover preserves high catalytic stability.

A structure-directing method to prepare semiconductive zeolitic cluster–organic frameworks with Cu3I4 building units

Co-reporter:Yao Kang, Wei-Hui Fang, Lei Zhang and Jian Zhang

Chemical Communications 2015 - vol. 51(Issue 43) pp:NaN8997-8997

Publication Date(Web):2015/04/21

DOI:10.1039/C5CC02598B

Two semiconductive cluster–organic frameworks based on Cu4I4 and Cu3I4 building units were obtained by the use of different organic structure-directing agents; the latter Cu3I4 nodes are tetrahedrally connected through 1,4-diazabicyclo[2.2.2]octane (DABCO) linkers and Cu–I bridges, giving rise to a zeolitic framework with SOD topology.

Synthetic investigation, structural analysis and photocatalytic study of a carboxylate–phosphonate bridged Ti18-oxo cluster

Co-reporter:Wei-Hui Fang, Lei Zhang and Jian Zhang

Dalton Transactions 2017 - vol. 46(Issue 3) pp:NaN807-807

Publication Date(Web):2016/12/08

DOI:10.1039/C6DT04474C

By the combination of carboxylate and phosphonate ligands, we herein report a nanosized H2[Ti18(μ3-O)14(μ2-O)6(O3P-Phen)2(PA)16(OPri)14] (PTC-51) (HPA = propionic acid, O3P-Phen = phenyl phosphonate), whose structure can be observed as the linkage of independent phosphonate supporting and carboxylate bridging hexanuclear Ti(IV) clusters. We also demonstrate a concise crystalline phase diagram, which shows the important effect of phosphonate and carboxylate ligand ratio during synthetic reactions. The photocatalytic H2 evolution activities of the obtained polyoxotitanate materials have been studied, with carboxylate-Ti6 presenting the maximum H2 production rate up to 267.78 μmol g−1 h−1.

Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by π-conjugated chromophores

Co-reporter:Nagaraju Narayanam, Wei-Hui Fang, Kalpana Chintakrinda, Lei Zhang and Jian Zhang

Chemical Communications 2017 - vol. 53(Issue 57) pp:NaN8080-8080

Publication Date(Web):2017/06/26

DOI:10.1039/C7CC04388K

Deep eutectic-solvothermal synthesis has been successfully employed to prepare four polyoxo-titanium clusters (PTCs), with nuclearity up to 28. The cluster cores obtained via this method are completely functionalized by conjugated ligands and display different photocatalytic H2 production activities.

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Abstract

Abstract