Co-reporter:Bartosz Marzec;Lei Zhang;Nianyong Zhu
Dalton Transactions 2017 vol. 46(Issue 19) pp:6456-6463
Publication Date(Web):2017/05/15
DOI:10.1039/C7DT00914C
A bio-inspired synthetic approach to unprecedented hybrid supramolecular assemblies [Ca(Me2hda)(H2O)3]·H2O (1) and [Ca(C12hda)(H2O)2]·H2O (2), that are stabilized by iminodiacetate-substituted organic ligands is reported. The results of the single-crystal X-ray analysis of 1 further allowed the use of electron microscopy to verify the supramolecular structure of the fibrous assemblies of 2 that incorporate extended alkyl-substituted ligand derivatives. 2 reveals interesting features that distinguish these soft structures from purely inorganic, brittle materials: meshes of nanobelts transform on solid supports to form homogeneous films covering extended, micro-sized areas. The use of the reported ligand system as a habit modifier for CaCO3 results in hierarchical calcite aggregates. The structure-influencing effects of the ligands and their supramolecular assemblies promote the formation of calcite disks that tessellate into hollow microspheres that contain distinctive openings.
Co-reporter:Colm Healy;Brendan Twamley;Munuswamy Venkatesan;Sebastian Schmidt;Thorfinnur Gunnlaugsson
Chemical Communications 2017 vol. 53(Issue 77) pp:10660-10663
Publication Date(Web):2017/09/26
DOI:10.1039/C7CC05498J
Two bi-metallic, organophosphonate-stabilised sandwich-type polyoxomolybdate clusters, [Mo6Cu4O16(OH)2(C4H9PO3)4(C5H5N)2 (CH3O)4(H2O)]2− and [Mo7Cu7O19(OH)(CH3O)7(C4H9PO3)6(C5H5N)2]2−, are reported. These compounds are accessed via the “top-down” in situ disassembly of the [Mo6O19]2− Lindqvist species into reactive oligomers, followed by subsequent reassembly with polynuclear CuII assemblies to form the reported compounds.
Co-reporter:Ayuk M. Ako;Chris S. Hawes;Brendan Twamley
CrystEngComm (1999-Present) 2017 vol. 19(Issue 6) pp:994-1000
Publication Date(Web):2017/02/06
DOI:10.1039/C6CE02493A
We report the synthesis of a simple 1D Mn-azopyridine-based coordination polymer, poly-[MnII(NO3)2(OH2)2(azopy)2]·2MeCN (1) (azopy = 4,4′-azobis(pyridine)) and its use as a convenient feedstock to afford two 3D coordination polymers, namely: poly-[MnII(azopy)2(CNAgCN)4] (2), and poly-[MnII2(pda)(Hpda)2(azopy)2(OH2)2]·2MeCN (3), (pdaH2 = 1,4-phenylenediacetic acid). The compounds have been characterised by elemental analysis, IR, PXRD, TGA and single crystal X-ray diffraction. Compound 1 is a 1D coordination polymer while 2 represents a 3-dimensional coordination polymer adopting 2-fold interpenetrated rutile (rtl) topology and 3 is a 5-connected 3-dimensional coordination polymer with boron nitride (bnn) topology.
Co-reporter:Theresa O. Chimamkpam, Rodolphe Clérac, Dmitri Mitcov, Brendan Twamley, Munuswamy Venkatesan and Wolfgang Schmitt
Dalton Transactions 2016 vol. 45(Issue 4) pp:1349-1353
Publication Date(Web):21 Dec 2015
DOI:10.1039/C5DT04820F
Comproportionation reactions between MnCl2 and KMnO4 in the presence of arsonate or phosphonate ligands promote the cation-assisted assembly of high-nuclearity, wheel-shaped or toroidal {Mn8} (1) and {Mn24} (2) complexes; the closely corresponding reaction systems provide insights into the complexation behaviour of homologous phosphonate/arsonate ligand species.
Co-reporter:Nianyong Zhu;Debobroto Sensharma;Paul Wix;Matthew J. Lennox;Tina Düren;Wai-Yeung Wong
European Journal of Inorganic Chemistry 2016 Volume 2016( Issue 13-14) pp:1939-1943
Publication Date(Web):
DOI:10.1002/ejic.201501194
Abstract
The synthesis and structure of a new, highly augmented {Cu2}-“paddlewheel”-based metal–organic framework (MOF) that is stabilized by tritopic benzoate ligands is reported. The structure adopts an uncommon, less symmetrical, (3,4)-connected net topology and represents a rare framework isomer of the extensively studied {Cu2}-based pto and tbo analogues related to the purely inorganic, solid-state structures of platinum oxide or the twisted boracite. The concomitant formation of three isomeric forms by using {Cu}2-“paddlewheel” complexes and a single triangular, trifunctional ligand is unique and stems from the rotational flexibility of the benzoate moieties. Computational analyses support the structural studies and underline that this observed net topology can give rise to an exceptionally high surface area (greater than 3500 m2/g) despite the triple-interpenetrated nature of the compound.
Co-reporter:Gerard Tobin, Steve Comby, Nianyong Zhu, Rodolphe Clérac, Thorfinnur Gunnlaugsson and Wolfgang Schmitt
Chemical Communications 2015 vol. 51(Issue 68) pp:13313-13316
Publication Date(Web):15 Jul 2015
DOI:10.1039/C5CC04928H
We report the synthesis, structure and physicochemical attributes of a new holmium(III)-based metal–organic framework whose 3D network structure gives rise to porosity; the reported structure-type can be varied using a range of different lanthanide ions to tune the photophysical properties and produce ligand-sensitised near-infrared (NIR) and visible light emitters.
Co-reporter:Nianyong Zhu, Matthew J. Lennox, Tina Düren and Wolfgang Schmitt
Chemical Communications 2014 vol. 50(Issue 32) pp:4207-4210
Publication Date(Web):25 Feb 2014
DOI:10.1039/C3CC49829H
The syntheses, calculated surface areas and N2 uptakes of two highly augmented {Cu}2 ‘paddlewheel’-based MOFs provide a direct comparison of tbo and pto framework polymorphs with identical composition.
Co-reporter:Mariyatra B. Mahimaidoss, Sergey A. Krasnikov, Lukas Reck, Camelia I. Onet, John M. Breen, Nianyong Zhu, Bartosz Marzec, Igor V. Shvets and Wolfgang Schmitt
Chemical Communications 2014 vol. 50(Issue 18) pp:2265-2267
Publication Date(Web):13 Dec 2013
DOI:10.1039/C3CC48541B
The dimensions and cavity sizes of the molecular capsules with the general formula [V10O18L4]10− can be controlled modularly through the nature of the bifunctional, rigid organophosphonate ligands L1 and L2 (L1 = bis(4-phosphonatophenyl)ethyne and L2 = bis(4-phosphonatophenyl)butadiyne); the solution stability of the molecular entities as demonstrated by ESI-MS studies permits their assembly on the Au(111) surface on a sub-monolayer scale giving rise to a 2D supramolecular structure that is comparable to the packing arrangements of the capsules in the crystal structures.
Co-reporter:Jian-Di Lin, Rodolphe Clérac, Mathieu Rouzières, Munuswamy Venkatesan, Theresa O. Chimamkpam and Wolfgang Schmitt
CrystEngComm 2014 vol. 16(Issue 34) pp:7894-7905
Publication Date(Web):03 Jun 2014
DOI:10.1039/C4CE00553H
This account describes the coordination chemistry of a novel bifunctional arsonic acid ligand, 4-(1,2,4-triazol-4-yl)phenylarsonic acid (H2TPAA) that contains a triazole group. Hydrothermal reactions of transition metal salts with H2TPAA produced five unprecedented coordination polymers: [Co(H2TPAA)(HTPAA)2]·H2O (1), M(HTPAA)Cl·2H2O (M = Cu (2), Co (3)) and M(HTPAA)2 (M = Mn (4), Cd (5)). These five polymers have been fully characterized by single crystal and powder X-ray diffraction, thermogravimetric analysis, infra-red spectroscopy and elemental analysis. Single crystal X-ray diffraction reveals that 1, 2 and 3 adopt 2-D layered structural motifs whereas 4 and 5 are 3-D frameworks. 1 and 3 are the first examples of arsonate-stabilised cobalt(II) coordination polymers. Likewise, 4 is recognised as the first record of a MnII arsonate coordination polymer with 3-D framework topology. Its isostructural Cd analogue 5 shows characteristic ligand-centered fluorescence properties. Magnetic measurements of 2 and 4 reveal predominant antiferromagnetic interactions between their respective spin centers while, in agreement with its chain structure, 3 exhibits one-dimensional magnetic behavior with weak ferromagnetic interactions between the spin centres.
Co-reporter:Dr. Nianyong Zhu;Matthew J. Lennox;Gerard Tobin;Lisa Goodman;Dr. Tina Düren; Wolfgang Schmitt
Chemistry - A European Journal 2014 Volume 20( Issue 13) pp:3595-3599
Publication Date(Web):
DOI:10.1002/chem.201304856
Abstract
A solid-state approach that takes advantage of the ordered 3D arrangement of active secondary building units allows the preparation of new interlocked MOFs that grow hetero-epitaxially on the crystal faces of a precursor phase that acts as a “topological blueprint”. The synthetic strategy is exemplified by using rigid acetylene-based ligands to produce highly augmented CuII acetate-based MOFs.
Co-reporter:Adam R. Patterson ; Wolfgang Schmitt ;Rachel C. Evans
The Journal of Physical Chemistry C 2014 Volume 118(Issue 19) pp:10291-10301
Publication Date(Web):May 1, 2014
DOI:10.1021/jp501359m
We report the solvothermal synthesis and characterization of the structure, morphology, and photoluminescence properties of a series of unprecedented layered, organic–inorganic lanthanide (LnIII) phosphonates based on tert-butyl- (But), 1-naphthalene (Naph)- and 4-biphenyl (Biphen)-phosphonic acid. Through systematic variation of the ligand and the LnIII, we discuss the key structure–property relationships that must be managed for the design of Ln-phosphonates with tailored functionality. Single crystal and X-ray powder diffraction studies revealed that the size and shape of the employed ligand affects the type of layered material that forms. In agreement with their molecular structures, two distinct crystal morphologies are observed, 1D nanorods and 2D platelets, demonstrating that the anisotropy in the crystal structure and the variable coordination behavior of the ligands is directly translated to the crystal growth. Judicious selection of the ligand enables us to switch-on Ln-centered photoluminescence in both the visible (EuIII, TbIII) and near-infrared (NdIII and YbIII) spectral regions. Notably, the presented Yb-phosphonates are rare examples of phosphonate-based near-infrared emitters. Furthermore, the EuIII spectral fingerprint provided unique insight into the coordination environment of the metal center, facilitating structural characterization where X-ray diffraction analysis was limited.
Co-reporter:Lei Zhang, Camelia I. Onet, Rodolphe Clérac, Mathieu Rouzières, Bartosz Marzec, Markus Boese, Munuswamy Venkatesan and Wolfgang Schmitt
Chemical Communications 2013 vol. 49(Issue 67) pp:7400-7402
Publication Date(Web):19 Jun 2013
DOI:10.1039/C3CC42954G
We present herein a novel method to prepare free-standing Dried Foam Films (DFFs) whereby individual polynuclear manganese complexes cover quantitatively the holes of micro-grids; the fabricated, homogeneous films have a cross-sectional thickness of only ca. 5 nm and are characterised by high mechanical stability.
Co-reporter:Lei Zhang, Bartosz Marzec, Rodolphe Clérac, Yanhui Chen, Hongzhou Zhang and Wolfgang Schmitt
Chemical Communications 2013 vol. 49(Issue 1) pp:66-68
Publication Date(Web):04 Sep 2012
DOI:10.1039/C2CC35486A
A novel hexanuclear {Mn6} coordination complex with octahedral topology has been prepared and was subsequently used as a building unit for the construction of coordination polymers and metal–organic gels; the latter exhibit thixotropic behavior and reversible sol–gel phase transitions.
Co-reporter:Lei Zhang;Rodolphe Clérac;Camelia I. Onet;Colm Healy
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 10-11) pp:1654-1658
Publication Date(Web):
DOI:10.1002/ejic.201201177
Abstract
A manganese-containing organic–inorganic hybrid polyoxomolybdate, (TBA)2[MnII6MoVI10(O)12(μ-O)14(μ3-O)4(tert-butyl-PO3)6(Ac)2(pyridine)4(H2O)6]·(CH3CN)6 (1; Ac = CH3COO, TBA = tetrabutylammonium), was synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and IR spectroscopy. Lindqvist hexamolybdate and manganese(III) acetylacetonate were used as starting Mo and Mn sources, respectively. Hexadecanuclear, mixed-metal 1 is characterized by a sandwich-type structural motif, whereby a central {Mn6} unit is capped by two {Mo5} moieties. In addition, six fully deprotonated tert-butylphosphonate ligands bridge these metal centers by adopting η1:η1:η2:μ4 binding modes. MALDI-MS studies demonstrated that 1 displays interesting fragmentation behavior involving a series of {Mn6Mo10}, {Mn6Mo9}, {Mn6Mo8}, {Mn6Mo7}, {Mn6Mo6}, {Mn6Mo5}, and {Mn6Mo4} moieties. Investigation of the magnetic properties of 1 highlights typical antiferromagnetic interactions between the MnII spin centers.
Co-reporter:Nianyong Zhu, Gerard Tobin and Wolfgang Schmitt
Chemical Communications 2012 vol. 48(Issue 30) pp:3638-3640
Publication Date(Web):10 Feb 2012
DOI:10.1039/C2CC17357C
Tri- and pentanuclear, kinetically stable SBUs were exploited for the preparation of the novel MOFs [Zn3(BTEB)2(DMF)2] and (Me2NH2)[Zn5(BTEB)3(μ3-OH)2(DMF)2]. The applied synthetic approach results in topologies that are stabilised by tritopic benzene-trisethynylbenzoic acid (BTEB) linkers giving rise to chiral frameworks with large pores or channels.
Co-reporter:John M. Breen, Lei Zhang, Raphaèle Clement, and Wolfgang Schmitt
Inorganic Chemistry 2012 Volume 51(Issue 1) pp:19-21
Publication Date(Web):December 6, 2011
DOI:10.1021/ic202104z
Two novel hybrid polyoxovanadates that are functionalized by (4-aminophenyl)arsonic acid ligands form upon the reduction of vanadates(V) in aqueous systems, whereby the underlying condensation reactions are influenced by the nature of the employed acid. In the presence of Cl– ions that derive from hydrochloric acid, a tetradecanuclear cage structure [VIV14O16(OH)8-(O3AsC6H4-4-NH2)10]4–, whose cavity contains stabilizing halide ions and water molecules, is obtained. When nitric acid is used, a decanuclear [V10O18(O3AsC6H4-4-NH2)7(DMF)2]5– cluster can be isolated. The latter organizes into a hexagonal packing arrangement in the solid state.
Co-reporter:John M. Breen, Rodolphe Clérac, Lei Zhang, Suzanne M. Cloonan, Elaine Kennedy, Martin Feeney, Thomas McCabe, D. Clive Williams and Wolfgang Schmitt
Dalton Transactions 2012 vol. 41(Issue 10) pp:2918-2926
Publication Date(Web):23 Jan 2012
DOI:10.1039/C2DT11153E
Herein we report the intra- and inter-molecular assembly of a {V5O9} subunit. This mixed-valent structural motif can be stabilised as [V5O9(L1–3)4]5−/9− (1–3) by a range of organoarsonate ligands (L1–L3) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure [V12O14(OH)4(L1)10]4− (4) where two modified convex building units are linked via two dimeric {O4VIV(OH)2VIVO4} moieties. Bi-functional phosphonate ligands, L4–L6 allow the intramolecular connectivity of the {V5O9} subunit to give hybrid capsules [V10O18(L4–6)4]10− (5–7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na8H2[6]·36H2O and Na8H2[7]·2DMF·29H2O.
Co-reporter:Dr. Lei Zhang;Dr. Rodolphe Clérac;Pierre Heijboer;Dr. Wolfgang Schmitt
Angewandte Chemie 2012 Volume 124( Issue 12) pp:3062-3066
Publication Date(Web):
DOI:10.1002/ange.201107358
Co-reporter:Dr. Lei Zhang;Dr. Rodolphe Clérac;Pierre Heijboer;Dr. Wolfgang Schmitt
Angewandte Chemie International Edition 2012 Volume 51( Issue 12) pp:3007-3011
Publication Date(Web):
DOI:10.1002/anie.201107358
Co-reporter:Dr. Lei Zhang;Dr. Rodolphe Clérac;Camelia I. Onet;Dr. Munuswamy Venkatesan;Pierre Heijboer;Dr. Wolfgang Schmitt
Chemistry - A European Journal 2012 Volume 18( Issue 44) pp:13984-13988
Publication Date(Web):
DOI:10.1002/chem.201202297
Co-reporter:Lei Zhang
Journal of the American Chemical Society 2011 Volume 133(Issue 29) pp:11240-11248
Publication Date(Web):June 17, 2011
DOI:10.1021/ja2024004
Supramolecular coordination cages provide unique restricted inner cavities that can be exploited for molecular recognition purposes and catalysis. Their syntheses often involve complex self-organization processes and rely on the identification of preorganized, kinetically stable building units that provide ligand-accessible coordination sites. Here we report a highly effective protocol for the successive buildup of symmetrical nanoscopic polyoxometalate (POM) cages. Our methodology takes advantage of a supramolecular templating effect and utilizes the structure-directing influence of octahedral {Xx(H2O)6–x} (X = Br–, Cl–; x = 2, 4, 6) assemblies that reside inside the hollow cluster shells and determine the arrangement of di- and tetranuclear vanadate units. The approach allows the preparation of a series of high-nuclearity POM cages that are characterized by {V16As8}, {V16As10}, {V20As8}, and {V24As8} core structures. In the latter cluster cage, the vanadium centers adopt a truncated octahedral topology. The formation of this Archimedean body is the direct result of the assembly of six square {V4O8} units that cap the vertices of the encapsulated Platonic {Cl6} octahedron. To the best of our knowledge, this {V24As8} cage is the largest hybrid vanadate cluster reported to date.
Co-reporter:Camelia I. Onet ; Lei Zhang ; Rodolphe Clérac ; J. Bernard Jean-Denis ; Martin Feeney ; Thomas McCabe
Inorganic Chemistry 2011 Volume 50(Issue 2) pp:604-613
Publication Date(Web):December 8, 2010
DOI:10.1021/ic101672t
We report here a facile synthetic and analytical approach that allows us to identify and characterize functionalized polyoxomolybdate clusters that form upon the partial reduction of MoVI salts in the presence of organoarsonate ligands. We demonstrated that electrospray ionization mass spectrometry, in combination with X-ray crystallography, provides an extremely powerful tool, allowing us to exploit slight perturbations of the ligand structures for the preparation of a series of unprecedented cluster compounds. Redox-active transition metals that adopt cubane or related structures are of particular interest because of their resemblance to active sites of enzymes. Our investigations underline the stability of the hybrid compounds in solution, an essential requirement for potential applications as catalysts. Supplemental analyses include measurements of the magnetic properties, NMR, IR, UV/vis, and bond-valence-sum analyses. Our results highlight the possibility of exploring real-time growth reactions of polyoxometales that emerge in solution and transform to produce hybrid organic−inorganic polyoxometalate clusters.
Co-reporter:David P. Walsh;Lei Zhang;Paul E. Kruger
Journal of Inorganic and Organometallic Polymers and Materials 2011 Volume 21( Issue 3) pp:
Publication Date(Web):2011 September
DOI:10.1007/s10904-011-9536-0
Two new network structures, K[NiII(Hadta)(H2O)2]·H2O (1) and K[Cu1.5II(adta)(H2O)1.5]·H2O (2) which are stabilized by 2-aminodiacetic terephthalic acid ligands have been synthesized and structurally characterized. Supplemental analyses include infrared spectroscopy and CHN analysis. 1 contains mononuclear secondary building units that are linked through potassium counterions and H-bonds to form a 3D network structure. 2 contains a 1D coordination polymer containing CuII ions with two different coordination environments. Potassium counterions further network these 1D chain structures.
Co-reporter:Wolfgang Schmitt, Lei Zhang, Christopher E. Anson and Annie K. Powell
Dalton Transactions 2010 vol. 39(Issue 42) pp:10279-10285
Publication Date(Web):30 Sep 2010
DOI:10.1039/C0DT00655F
An approach for the preparation of oxy/hydroxy briged FeIII clusters that takes advantage of hydrolytic condensations of well defined {Fe2hpdta(H2O)4} building units is presented. Co-ligands such as tripodal H3tea or bidentate organic bases such as ethylenediamine (enH2) can be used to complete the coordination spheres of the FeIII centres and stabilise unsymmetrical iron-oxo clusters with non-zero magnetic ground spin-states. This strategy led to the isolation of a pentanuclear complex [Fe5(μ3-O)(hpdta)(H2tea)(Htea)2)(tea)]·{N(C2H4OH)3}·2EtOH·7H2O (1) and a nonanuclear coordination complex [Fe9(μ3-O)5(μ-OH)5(en)6(hpdta)2](NO3)2·7H2O (2).
Co-reporter:David P. Walsh, Rodolphe Clérac, Nigel G. R. Hearns, Paul E. Kruger and Wolfgang Schmitt
CrystEngComm 2009 vol. 11(Issue 8) pp:1666-1673
Publication Date(Web):29 Apr 2009
DOI:10.1039/B902010A
We describe a synthetic methodology to prepare 1D coordination polymers using 5-aminodiacetic isophthalic acid (H4adip) as chelating agent and 2,2′-bipyridine (bpy) as an auxiliary ligand. The function of the latter is to block two coordination sites on the metal(II) centres thus avoiding the formation of 3D networks and directing the assembly into low dimensional networks. The compounds [CoII2(adip)(bpy)(H2O)4]·3H2O (1), [NiII2(adip)(bpy)(H2O)4]·3H2O (2) and [CuII(H2adip)(bpy)] (3) were synthesised under hydrothermal reaction conditions with the motivation to investigate spin interactions in these 1D chain structures. We report the structures of the compounds and investigate and model their magnetic properties. The supramolecular structures of 1–3 are characterised by inter- and intra-chain π–π interactions and hydrogen bonding.
Co-reporter:JohnM. Breen Dr.
Angewandte Chemie 2008 Volume 120( Issue 36) pp:7010-7014
Publication Date(Web):
DOI:10.1002/ange.200801770
Co-reporter:JohnM. Breen Dr.
Angewandte Chemie International Edition 2008 Volume 47( Issue 36) pp:6904-6908
Publication Date(Web):
DOI:10.1002/anie.200801770
Co-reporter:Giuseppe La Spina, Rodolphe Clérac, Emily S. Collins, Thomas McCabe, Munuswamy Venkatesan, Izumi Ichinose and Wolfgang Schmitt
Dalton Transactions 2007 (Issue 45) pp:5248-5252
Publication Date(Web):19 Oct 2007
DOI:10.1039/B710828A
Hybrid organic-inorganic coordination assemblies are synthesized using modified aminocarboxylic acid ligands as the structure-directing agents. The synthetic approach results in two novel dinuclear copper(II) complexes, K2[CuII(hnida)]2·2H2O (1) and K4[CuII(chnida)]2·4H2O·4MeOH (2) that assemble in the presence of suitable counterions into a densely packed hexagonal array or an open-framework structure. The functionality of the aminocarboxylic acid ligands provides a tool to control the supramolecular structure. The materials combine promising thermal stabilities with the necessary flexibility to withstand structural changes induced by calcinations or the uptake and release of guest molecules. The structural and physicochemical properties of the complexes were investigated using X-ray diffraction, magnetic measurements, thermogravimetric analysis and spectroscopy.
Co-reporter:Ian McKeogh, Jonathan P. Hill, Emily S. Collins, Thomas McCabe, Annie K. Powell and Wolfgang Schmitt
New Journal of Chemistry 2007 vol. 31(Issue 11) pp:1882-1886
Publication Date(Web):25 Sep 2007
DOI:10.1039/B711185A
We report a synthetic approach for the assembly of FeIII complexes via hydrogen bonded water aggregates to give coordination networks that contain separated hydrophobic organic and hydrophilic inorganic areas; the amphiphilicity of the reaction system allows assembly into nanosized vesicular spheres that obey the building principles of the related crystalline solids.
Co-reporter:Gerard Tobin, Steve Comby, Nianyong Zhu, Rodolphe Clérac, Thorfinnur Gunnlaugsson and Wolfgang Schmitt
Chemical Communications 2015 - vol. 51(Issue 68) pp:NaN13316-13316
Publication Date(Web):2015/07/15
DOI:10.1039/C5CC04928H
We report the synthesis, structure and physicochemical attributes of a new holmium(III)-based metal–organic framework whose 3D network structure gives rise to porosity; the reported structure-type can be varied using a range of different lanthanide ions to tune the photophysical properties and produce ligand-sensitised near-infrared (NIR) and visible light emitters.
Co-reporter:Mariyatra B. Mahimaidoss, Sergey A. Krasnikov, Lukas Reck, Camelia I. Onet, John M. Breen, Nianyong Zhu, Bartosz Marzec, Igor V. Shvets and Wolfgang Schmitt
Chemical Communications 2014 - vol. 50(Issue 18) pp:NaN2267-2267
Publication Date(Web):2013/12/13
DOI:10.1039/C3CC48541B
The dimensions and cavity sizes of the molecular capsules with the general formula [V10O18L4]10− can be controlled modularly through the nature of the bifunctional, rigid organophosphonate ligands L1 and L2 (L1 = bis(4-phosphonatophenyl)ethyne and L2 = bis(4-phosphonatophenyl)butadiyne); the solution stability of the molecular entities as demonstrated by ESI-MS studies permits their assembly on the Au(111) surface on a sub-monolayer scale giving rise to a 2D supramolecular structure that is comparable to the packing arrangements of the capsules in the crystal structures.
Co-reporter:Giuseppe La Spina, Rodolphe Clérac, Emily S. Collins, Thomas McCabe, Munuswamy Venkatesan, Izumi Ichinose and Wolfgang Schmitt
Dalton Transactions 2007(Issue 45) pp:NaN5252-5252
Publication Date(Web):2007/10/19
DOI:10.1039/B710828A
Hybrid organic-inorganic coordination assemblies are synthesized using modified aminocarboxylic acid ligands as the structure-directing agents. The synthetic approach results in two novel dinuclear copper(II) complexes, K2[CuII(hnida)]2·2H2O (1) and K4[CuII(chnida)]2·4H2O·4MeOH (2) that assemble in the presence of suitable counterions into a densely packed hexagonal array or an open-framework structure. The functionality of the aminocarboxylic acid ligands provides a tool to control the supramolecular structure. The materials combine promising thermal stabilities with the necessary flexibility to withstand structural changes induced by calcinations or the uptake and release of guest molecules. The structural and physicochemical properties of the complexes were investigated using X-ray diffraction, magnetic measurements, thermogravimetric analysis and spectroscopy.
Co-reporter:Wolfgang Schmitt, Lei Zhang, Christopher E. Anson and Annie K. Powell
Dalton Transactions 2010 - vol. 39(Issue 42) pp:NaN10285-10285
Publication Date(Web):2010/09/30
DOI:10.1039/C0DT00655F
An approach for the preparation of oxy/hydroxy briged FeIII clusters that takes advantage of hydrolytic condensations of well defined {Fe2hpdta(H2O)4} building units is presented. Co-ligands such as tripodal H3tea or bidentate organic bases such as ethylenediamine (enH2) can be used to complete the coordination spheres of the FeIII centres and stabilise unsymmetrical iron-oxo clusters with non-zero magnetic ground spin-states. This strategy led to the isolation of a pentanuclear complex [Fe5(μ3-O)(hpdta)(H2tea)(Htea)2)(tea)]·{N(C2H4OH)3}·2EtOH·7H2O (1) and a nonanuclear coordination complex [Fe9(μ3-O)5(μ-OH)5(en)6(hpdta)2](NO3)2·7H2O (2).
Co-reporter:John M. Breen, Rodolphe Clérac, Lei Zhang, Suzanne M. Cloonan, Elaine Kennedy, Martin Feeney, Thomas McCabe, D. Clive Williams and Wolfgang Schmitt
Dalton Transactions 2012 - vol. 41(Issue 10) pp:NaN2926-2926
Publication Date(Web):2012/01/23
DOI:10.1039/C2DT11153E
Herein we report the intra- and inter-molecular assembly of a {V5O9} subunit. This mixed-valent structural motif can be stabilised as [V5O9(L1–3)4]5−/9− (1–3) by a range of organoarsonate ligands (L1–L3) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure [V12O14(OH)4(L1)10]4− (4) where two modified convex building units are linked via two dimeric {O4VIV(OH)2VIVO4} moieties. Bi-functional phosphonate ligands, L4–L6 allow the intramolecular connectivity of the {V5O9} subunit to give hybrid capsules [V10O18(L4–6)4]10− (5–7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na8H2[6]·36H2O and Na8H2[7]·2DMF·29H2O.
Co-reporter:Lei Zhang, Camelia I. Onet, Rodolphe Clérac, Mathieu Rouzières, Bartosz Marzec, Markus Boese, Munuswamy Venkatesan and Wolfgang Schmitt
Chemical Communications 2013 - vol. 49(Issue 67) pp:NaN7402-7402
Publication Date(Web):2013/06/19
DOI:10.1039/C3CC42954G
We present herein a novel method to prepare free-standing Dried Foam Films (DFFs) whereby individual polynuclear manganese complexes cover quantitatively the holes of micro-grids; the fabricated, homogeneous films have a cross-sectional thickness of only ca. 5 nm and are characterised by high mechanical stability.
Co-reporter:Lei Zhang, Bartosz Marzec, Rodolphe Clérac, Yanhui Chen, Hongzhou Zhang and Wolfgang Schmitt
Chemical Communications 2013 - vol. 49(Issue 1) pp:NaN68-68
Publication Date(Web):2012/09/04
DOI:10.1039/C2CC35486A
A novel hexanuclear {Mn6} coordination complex with octahedral topology has been prepared and was subsequently used as a building unit for the construction of coordination polymers and metal–organic gels; the latter exhibit thixotropic behavior and reversible sol–gel phase transitions.
Co-reporter:Nianyong Zhu, Gerard Tobin and Wolfgang Schmitt
Chemical Communications 2012 - vol. 48(Issue 30) pp:NaN3640-3640
Publication Date(Web):2012/02/10
DOI:10.1039/C2CC17357C
Tri- and pentanuclear, kinetically stable SBUs were exploited for the preparation of the novel MOFs [Zn3(BTEB)2(DMF)2] and (Me2NH2)[Zn5(BTEB)3(μ3-OH)2(DMF)2]. The applied synthetic approach results in topologies that are stabilised by tritopic benzene-trisethynylbenzoic acid (BTEB) linkers giving rise to chiral frameworks with large pores or channels.
Co-reporter:Nianyong Zhu, Matthew J. Lennox, Tina Düren and Wolfgang Schmitt
Chemical Communications 2014 - vol. 50(Issue 32) pp:NaN4210-4210
Publication Date(Web):2014/02/25
DOI:10.1039/C3CC49829H
The syntheses, calculated surface areas and N2 uptakes of two highly augmented {Cu}2 ‘paddlewheel’-based MOFs provide a direct comparison of tbo and pto framework polymorphs with identical composition.
Co-reporter:Lei Zhang, Theresa Chimamkpam, Camelia I. Onet, Nianyong Zhu, Rodolphe Clérac and Wolfgang Schmitt
Dalton Transactions 2016 - vol. 45(Issue 44) pp:NaN17713-17713
Publication Date(Web):2016/10/11
DOI:10.1039/C6DT02642G
We report a supramolecular approach to mixed-valent Mn coordination clusters that demonstrates how halide ions can be applied to influence the assembly of distinct tetranuclear building units to produce a number of related Mn coordination clusters with dense core structures that derive from a cuboctahedral arrangement of Mn ions. In all compounds the alignment of the Jahn–Teller axes of the MnIII centers coincides with the positions of the stabilizing chloride ligands. Thus, the relative chloride concentrations in the reaction mixtures allow us to modify the symmetry and magnetic anisotropy of this basic core structures resulting in isotropic polynuclear high-spin complexes at high Cl− concentrations and Single-Molecule Magnets at lower relative Cl− concentrations.
Co-reporter:Bartosz Marzec, Lei Zhang, Nianyong Zhu and Wolfgang Schmitt
Dalton Transactions 2017 - vol. 46(Issue 19) pp:NaN6463-6463
Publication Date(Web):2017/04/20
DOI:10.1039/C7DT00914C
A bio-inspired synthetic approach to unprecedented hybrid supramolecular assemblies [Ca(Me2hda)(H2O)3]·H2O (1) and [Ca(C12hda)(H2O)2]·H2O (2), that are stabilized by iminodiacetate-substituted organic ligands is reported. The results of the single-crystal X-ray analysis of 1 further allowed the use of electron microscopy to verify the supramolecular structure of the fibrous assemblies of 2 that incorporate extended alkyl-substituted ligand derivatives. 2 reveals interesting features that distinguish these soft structures from purely inorganic, brittle materials: meshes of nanobelts transform on solid supports to form homogeneous films covering extended, micro-sized areas. The use of the reported ligand system as a habit modifier for CaCO3 results in hierarchical calcite aggregates. The structure-influencing effects of the ligands and their supramolecular assemblies promote the formation of calcite disks that tessellate into hollow microspheres that contain distinctive openings.
Co-reporter:Theresa O. Chimamkpam, Rodolphe Clérac, Dmitri Mitcov, Brendan Twamley, Munuswamy Venkatesan and Wolfgang Schmitt
Dalton Transactions 2016 - vol. 45(Issue 4) pp:NaN1353-1353
Publication Date(Web):2015/12/21
DOI:10.1039/C5DT04820F
Comproportionation reactions between MnCl2 and KMnO4 in the presence of arsonate or phosphonate ligands promote the cation-assisted assembly of high-nuclearity, wheel-shaped or toroidal {Mn8} (1) and {Mn24} (2) complexes; the closely corresponding reaction systems provide insights into the complexation behaviour of homologous phosphonate/arsonate ligand species.
![Phosphonic acid, [1,1'-biphenyl]-4-yl-](http://img.cochemist.com/ccimg/78000/77918-47-9.png)
![Phosphonic acid, [1,1'-biphenyl]-4-yl-](http://img.cochemist.com/ccimg/78000/77918-47-9_b.png)
![[HYDROXY(OXIDO)PHOSPHORYL] PHOSPHATE](/data/chemimg/63300/42499-21-8.png)
![[HYDROXY(OXIDO)PHOSPHORYL] PHOSPHATE](/data/chemimg/63300/42499-21-8_b.png)
