Michaele J. Hardie

M12L8 metallo-supramolecular cube with cyclotriguaiacylene-type ligand: spontaneous resolution of cube and its constituent host ligand

Co-reporter:Jonathan M. Fowler, Flora L. Thorp-Greenwood, Stuart L. Warriner, Charlotte E. Willans and Michaele J. Hardie

Chemical Communications 2016 vol. 52(Issue 56) pp:8699-8702

Publication Date(Web):22 Jun 2016

DOI:10.1039/C6CC04130B

The racemic ligand (±)-tris-(4-methylthiazolyl)cyclotriguaiacylene forms a homochiral crystalline Ag12L8 cube with spontaneous resolution. The ligand itself likewise crystallises in a chirally pure fashion in two clathrate complexes. Ag12L8 is the first example of a cyclotriguaiacylene-type coordination cube and a rare example of a M12L8-type metallo-cube.

Tris(rhenium fac-tricarbonyl) Polypyridine Functionalized Cyclotriguaiacylene Ligands with Rich and Varied Emission

Co-reporter:Flora L. Thorp-Greenwood, Victoria E. Pritchard, Michael P. Coogan, and Michaele J. Hardie

Organometallics 2016 Volume 35(Issue 11) pp:1632-1642

Publication Date(Web):May 26, 2016

DOI:10.1021/acs.organomet.6b00099

Trinuclear rhenium fac-tricarbonyl bromide complexes have been synthesized coordinated to the host ligands tris(4-[4-methyl-2,2′-bipyridyl]methyl)cyclotriguaiacylene (L1), tris(4-[4-methyl-2,2′-bipyridoyl])cyclotriguaiacylene (L2), and tris(4-[2,2′,6′,2″-terpyridyl]benzyl)cyclotriguaiacylene (L3). The structure of L1 and complexes [{Re(CO)3Br}3(L1)] (1) and [{Re(CO)3Br}3(L3)] (3) have been elucidated through X-ray single-crystal diffraction, with complex 3 crystallizing as a conglomerate. The steady-state luminescent properties and time-resolved fluorescence studies of the complexes have been conducted and revealed an unusual dual-emission phenomenon for complex 2. Complexes 1 and 2 show red-shifted emission wavelengths in comparison with those typical of monometallic Re(CO)3-bipy-Br complexes, while complex 3 showed an unusual excitation-dependent variation of emission wavelength.

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies

Co-reporter:Flora L. Thorp-Greenwood, Tanya K. Ronson and Michaele J. Hardie

Chemical Science 2015 vol. 6(Issue 10) pp:5779-5792

Publication Date(Web):14 Jul 2015

DOI:10.1039/C5SC01801C

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI4CuII1.5(L1)3(CN)6]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu3(L2)4(H2O)3]·6(OTf)·n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (43.123)(42.122) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII analogue [Cu2(L1)2(NMP)(H2O)]·4BF4·12NMP·1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.82 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C60 through soaking the crystals in a toluene solution.

Controlling the assembly of cyclotriveratrylene-derived coordination cages

Co-reporter:James J. Henkelis and Michaele J. Hardie

Chemical Communications 2015 vol. 51(Issue 60) pp:11929-11943

Publication Date(Web):10 Jun 2015

DOI:10.1039/C5CC03071D

A review of the emerging field of cyclotriveratrylene-derived coordination cages is presented. Ligand-functionalised cyclotriveratrylene (CTV) derivatives self-assemble with a range of metal cations to afford coordination cages, polymers and topologically non-trivial constructs, such as [2]catenanes and a self-entangled cube. Increased control over their self-assembly allows for the controlled and predictable formation of well-defined coordination cages for application in host–guest and recognition chemistry, with surfactant binding and single-crystal-to-single-crystal (SCTSC) uptake of small-molecule guests being observed.

Metallo-Cryptophanes Decorated with Bis-N-Heterocyclic Carbene Ligands: Self-Assembly and Guest Uptake into a Nonporous Crystalline Lattice

Co-reporter:James J. Henkelis ; Christopher J. Carruthers ; Scott E. Chambers ; Rob Clowes ; Andrew I. Cooper ; Julie Fisher

Journal of the American Chemical Society 2014 Volume 136(Issue 41) pp:14393-14396

Publication Date(Web):October 3, 2014

DOI:10.1021/ja508502u

Pd3L2 metallo-cryptophane cages with cyclotriveratrylene-type L ligands can be stabilized by use of a bis-N-heterocyclic carbene as an auxiliary cis-protecting ligand, while use of more common protecting chelating ligands such as ethylenediamine saw a Pd3L2 to Pd6L8 rearrangement occur in solution. The crystalline Pd3L2 complexes act as sponges, taking up 1,2-dichorobenzene or iodine in a single-crystal-to-single-crystal fashion despite not exhibiting conventional porosity.

Three-Dimensional Silver-dabco Coordination Polymers with Zeolitic or Three-Connected Topology

Co-reporter:Flora L. Thorp-Greenwood, Alexander N. Kulak, and Michaele J. Hardie

Crystal Growth & Design 2014 Volume 14(Issue 11) pp:5361-5365

Publication Date(Web):October 21, 2014

DOI:10.1021/cg501231v

The simple linear linking ligand diazabicyclo[2.2.2]octane (dabco) combines with silver(I) to form three-dimensional (3D) coordination polymers which have either a zeolitic mtn topology structure or a (10,3)-b ths network according to the counteranion used. The tetrahedral anions BF4– or ReO4– promote formation of [Ag(dabco)2]·X, which has a 3D four-connected mtn framework of fused 512 and 64512 cages, and the material shows modest absorption of iodine. The bulky anion [Co(C2B9H11)2]− and an excess of dabco promote formation of complex [Ag2(dabco)3(CH3CN)2]·2[Co(C2B9H11)2] with a three-connected (10,3)-b network, while use of 1 equiv of dabco gives a previously reported [Ag(dabco)]·[Co(C2B9H11)2], which has a one-dimensional coordination chain structure.

Lanthanide coordination polymers with pyridyl-N-oxide or carboxylate functionalised host ligands

Co-reporter:James J. Henkelis, Tanya K. Ronson and Michaele J. Hardie

CrystEngComm 2014 vol. 16(Issue 18) pp:3688-3693

Publication Date(Web):13 Aug 2013

DOI:10.1039/C3CE40776D

The first examples of coordination polymers of hard-donor functionalised cyclotriveratrylene ligands with the lanthanide(III) cations are reported, these include 1D 3-connected ladder structures and a 2D decorated kagome dual.

Tuning the coordination chemistry of cyclotriveratrylene ligand pairs through alkyl chain aggregation

Co-reporter:James J. Henkelis and Michaele J. Hardie

CrystEngComm 2014 vol. 16(Issue 35) pp:8138-8146

Publication Date(Web):10 Jun 2014

DOI:10.1039/C4CE00467A

Propylated cyclotriveratrylene (CTV) ligands display different coordination chemistry over their methylated congeners as a result of increased solubility, an affinity for alkyl chain aggregation and steric factors. The propylated ligand tris(isonicotinoyl)-tris(propoxy)-cyclotricatechylene (L1p) forms a 1D coordination polymer within complex {[Ag(L1p)[Co(C2B9H11)2]](DMF)}∞ (complex 1p), and a 2D sheet of 4·82 topology in {[Cd(L1p)(ONO2)2(H2O)]·(DMF)·0.5(Et2O)}∞ (complex 2p), neither of which are formed with the analogous methylated ligand tris(isonicotinoyl)-cyclotriguaiacylene (L1m). Both complexes 1p and 2p display multiple sites of aggregation of hydrophobic groups. The new propylated ligand tris(2-quinolylmethyl)-tris(propoxy)-cyclotricatechylene (L2p) forms a 1D coordination polymer with Ag(I) in complex{[Ag2(L2p)2][Co(C2B9H11)2]2·1.5(MeNO2)}∞ (complex 3p) and a novel, compressed octahedral structure with palladium(II) cations, [Pd6(L2p)4(CF3CO2)12] (complex 4p). Neither complex was accessible with the methylated congener tris(2-quinolylmethyl)-cyclotriguaiacylene (L2m).

Hexasulfanyl analogues of cyclotriveratrylene

Co-reporter:Marc A. Little, Jonathan J. Loughrey, Amedeo Santoro, Malcolm A. Halcrow, Michaele J. Hardie

Tetrahedron Letters 2014 Volume 55(Issue 15) pp:2530-2533

Publication Date(Web):9 April 2014

DOI:10.1016/j.tetlet.2014.03.025

The synthesis of four 3,4-di(alkylsulfanyl)benzyl alcohol derivatives is described, in five steps from methyl 3,4-di(hydroxy)benzoate via a Newman–Kwart rearrangement. Incubation of these derivatives in formic acid affords 2,3,7,8,12,13-hexakis(alkylsulfanyl)-10,15-dihydro-5H-tribenzo[a,d,g]cyclononene products, which are hexa-sulfanyl analogues of the well-known supramolecular cavitand host, cyclotriveratrylene (CTV). The yield of this cyclization depends strongly on the alkylsulfanyl substituents present, in the order SMe > SEt ≈ SiPr ≫ SBn. A crystal structure determination of one of the cyclotrimers shows a mode of self-association that is commonly exhibited by CTV itself.

Solvent-Dependent Self-Assembly Behaviour and Speciation Control of Pd6L8 Metallo-supramolecular Cages

Co-reporter:James J. Henkelis;Dr. Julie Fisher;Dr. Stuart L. Warriner ; Michaele J. Hardie

Chemistry - A European Journal 2014 Volume 20( Issue 14) pp:4117-4125

Publication Date(Web):

DOI:10.1002/chem.201304437

Abstract

The C₃-symmetric chiral propylated host-type ligands (±)-tris(isonicotinoyl)-tris(propyl)-cyclotricatechylene (L1) and (±)-tris(4-pyridyl-4-benzoxy)-tris(propyl)-cyclotricatechylene (L2) self-assemble with Pd^II into [Pd₆L₈]¹²⁺ metallo-cages that resemble a stella octangula. The self-assembly of the [Pd₆(L1)₈]¹²⁺ cage is solvent-dependent; broad NMR resonances and a disordered crystal structure indicate no chiral self-sorting of the ligand enantiomers in DMSO solution, but sharp NMR resonances occur in MeCN or MeNO₂. The [Pd₆(L1)₈]¹²⁺ cage is observed to be less favourable in the presence of additional ligand, than is its counterpart, where L=(±)-tris(isonicotinoyl)cyclotriguaiacylene (L1 a). The stoichiometry of reactant mixtures and chemical triggers can be used to control formation of mixtures of homoleptic or heteroleptic [Pd₆L₈]¹²⁺ metallo-cages where L=L1 and L1 a.

A bis(disulfide)-linked offset cryptophane

Co-reporter:Marc A. Little, Malcolm A. Halcrow and Michaele J. Hardie

Chemical Communications 2013 vol. 49(Issue 15) pp:1512-1514

Publication Date(Web):17 Jan 2013

DOI:10.1039/C3CC38768B

A new bis(disulfide)-linked offset dimer is formed from a dithiolated analogue of cyclotriguaiacylene. Unlike a similar tris(disulfide)-linked example, this is not a true cryptophane as the offset nature of the dimerisation and intramolecular host–guest interactions preclude its use as a host.

Silver-Dabco Coordination Networks with Distinct Carbaborane Anions: Investigating Ag···H–B and Ag···I–B Interactions

Co-reporter:Luís Cunha-Silva, Michael J. Carr, John D. Kennedy, and Michaele J. Hardie

Crystal Growth & Design 2013 Volume 13(Issue 7) pp:3162-3170

Publication Date(Web):May 13, 2013

DOI:10.1021/cg4005328

A novel series of metal–organic frameworks (MOFs) based on Ag(I) and the nitrogen-bridging ligand 1,4-diazabicyclo[2.2.2]octane (dabco) along with the incorporation of distinct carbaborane anions were synthesized and isolated as crystalline materials. Single-crystal X-ray diffraction analysis unveiled novel materials formulated as [Ag(dabco)][Cobdc] (1), [Ag(dabco)(PhCB9H9)] (2), [Ag(dabco)(PhCB9H8I)] (3), and [Ag(dabco)(PhCB11H5I6)] (4), which were further characterized by Fourier-transform infrared spectroscopy and elemental analysis. Interestingly, despite the use of distinct carbaborane anions, all the materials feature one-dimensional (1D) coordination networks with most of the bulky anions, particularly all the phenyl-carbaborane anion [PhCB9H9]−, [PhCB9H8I]−, and [PhCB11H5I6]−, incorporated in the coordination networks through Ag···H–B coordinative interactions or Ag···I–B coordination bonds. However, the influence of the distinct carbaborane anions is clearly reflected in the coordination features of Ag(I) centers, since all of them are engaged in different combinations of interactions (coordination bonds Ag–N and Ag–I and both coordinative or electrostatic Ag···H–B interactions) and in the overall characteristics of the 1D coordination networks.

Coordination Polymers Utilizing N-Oxide Functionalized Host Ligands

Co-reporter:James J. Henkelis, Sarah A. Barnett, Lindsay P. Harding, and Michaele J. Hardie

Inorganic Chemistry 2012 Volume 51(Issue 20) pp:10657-10674

Publication Date(Web):September 27, 2012

DOI:10.1021/ic300940k

Pyridyl functionalized host molecules are oxidized to their N-oxide analogues and form a series of coordination polymers and discrete complexes with transition metal cations. Complex {[Ag3(NMP)6(L1)2]·3(ClO4)}∞ where L1 = tris(isonicotinoyl-N-oxide)cyclotriguaiacylene, NMP = N-methylpyrrolidone, is a three-dimensional (3-D) 3,6-connected coordination polymer of pyrite-like (pyr) topology and features ligand unsupported argentophilic interactions, while two-dimensional (2-D) 3,6-connected coordination polymers with the rarely reported kagome dual (kgd) topology are found for [M(L1)2]2+ where M = Zn, Cd, Cu. Ligand L2 = tris(nicotinoyl-N-oxide)cyclotriguaiacylene forms a 2-D coordination polymer with 44 (sql) grid topology in complexes {[M(L2)2(DMF)2]·2ClO4·8(DMF)}∞ M = Cd or Cu, DMF = N,N′-dimethylformamide, and a double-linked chain structure in {[Co(L2)2(DMF)2]·2NO3·4(DMF)·H2O}∞, and both types of structure feature hand-shake self-inclusion motifs either within or between the polymers. 2-D coordination networks with 63 (hcb) topologies are found in complexes {[M(L3)(NO3)2]·2(DMF)}∞ (M = Cd, Zn) and {[Cu5(L3)2Cl10(NMP)4]}∞ where L3 = tris(2-pyridylmethyl)cyclotriguaiacylene, while [Ag2(L3)2(NMP)4]·2(BF4)·2(NMP) has a discrete dimeric structure which again shows hand-shake host–guest interactions supported by π–π stacking.

Exploring Ag⋯H–B interactions in coordination polymers: silver–alkanedinitrile networks with cobalt carbaborane anions

Co-reporter:Luís Cunha-Silva and Michaele J. Hardie

CrystEngComm 2012 vol. 14(Issue 10) pp:3367-3372

Publication Date(Web):16 Feb 2012

DOI:10.1039/C2CE00003B

Uncommon silver coordination environments occupied exclusively by Ag⋯H–B interactions, namely Ag⋯(H–B)4 and Ag⋯(H–B)6 centres, were observed in two novel coordination polymers, [Ag(pim)(Cobdc)][Ag(Cobdc)] (1) (pim = pimelonitrile, CN(CH2)5CN, and Cobdc = cobalt(III) bis(dicarbollide) anion, [Co(C2B9H11)2]−) and [Ag3(sub)2(Cobdc)3] (2) (sub = suberonitrile, CN(CH2)6CN). The Ag⋯(H–B)4 centre was observed in compound 1 and shows a geometry that resembles an extremely distorted tetrahedron, while a highly distorted octahedral centre Ag⋯(H–B)6 was found in 2. The two compounds were isolated as crystalline materials, their structures established by single crystal X-ray diffraction and also characterized by CHN elemental analysis and infrared spectroscopy. The compounds 1 and 2 feature neutral 1D and 2D coordination polymers, [Ag(pim)(Cobdc)]1∞ and [Ag3(sub)2(Cobdc)3]2∞, respectively.

Metal Complexes of 2,2′-Bipyridine-4,4′-diamine as Metallo-Tectons for Hydrogen Bonded Networks

Co-reporter:Nicola Rigby, Tia Jacobs, Jayarama Prakasha Reddy, and Michaele J. Hardie

Crystal Growth & Design 2012 Volume 12(Issue 4) pp:1871-1881

Publication Date(Web):March 19, 2012

DOI:10.1021/cg201512q

Transition metal complexes of the ligand 2,2′-bipyridine-4,4′-diamine (bpy4da) form three-dimensional (3D) hydrogen bonding networks with the [M(bpy4da)3]2+ species, a hydrogen donor metallo-tecton with carboxylate counteranions as hydrogen bond acceptors within the complexes [[Ni(bpy4da)3]·(Hbpc)(bpc)0.5(dmf)n, [Ni(bpy4da)3].(bpc)(dmf)n, and [Ni(bpy4da)3]·(Htma)·4(dmf) where H2bpc = biphenyl-4,4′-dicarboxylic acid, H3tma = trimesic acid, and dmf = dimethylformamide. Terephthalate, on the other hand, bridges between Cu(II) centers in complexes [Cu2(bpy4da)4(tpa)]·2(NO3)·5(dmf) and [Cu2(bpy4da)4(tpa)]·2(NO3)·4.5(dmf)·(H2O) (where H2tpa = terephthalic acid) whose structures both feature different 3D hydrogen bonded networks. The crystal structures of hydrated [Cd(bpy4da)3]·2Cl and [Co(bpy4da)2(NO3)]2·2(NO3)·4.5(dmf) are also reported.

Synthesis and Methane-Binding Properties of Disulfide-Linked Cryptophane-0.0.0

Co-reporter:Marc A. Little;Jessica Donkin;Dr. Julie Fisher; Malcolm A. Halcrow;Jordan Loder ;Dr. Michaele J. Hardie

Angewandte Chemie International Edition 2012 Volume 51( Issue 3) pp:764-766

Publication Date(Web):

DOI:10.1002/anie.201106512

A Chiral, Self-Catenating and Porous MetalOrganic Framework and its Post-Synthetic Metal Uptake

Co-reporter:Dr. Tia Jacobs;Rob Clowes; Andrew I. Cooper;Dr. Michaele J. Hardie

Angewandte Chemie International Edition 2012 Volume 51( Issue 21) pp:5192-5195

Publication Date(Web):

DOI:10.1002/anie.201200758

Construction of MetalOrganic Frameworks: Versatile Behaviour of a Ligand Containing Mono- and Bidentate Coordination Sites

Co-reporter:Dr. Tia Jacobs ;Dr. Michaele J. Hardie

Chemistry - A European Journal 2012 Volume 18( Issue 1) pp:267-276

Publication Date(Web):

DOI:10.1002/chem.201101998

Abstract

Five new coordination polymers based on a new 2,2′-bipyridine derived ligand N,N′-bis(pyridin-4-yl)-2,2′-bipyridine-5,5′-dicarboxamide (=L) are reported herein. Isostructural three-dimensional coordination polymers with a rare (4,6)-connected network of {4⁴.6²}₃{4⁶.8⁹}₂ topology were synthesised from Cu(NO₃)₂, Zn(NO₃)₂ or a mixture of Cu(NO₃)₂/Fe(BF₄)₂ with L in complexes {[Cu₅L₆]⋅(NO₃)₁₀⋅(H₂O)₁₈}_∞ (1), {[Zn₅L₆]⋅(NO₃)₁₀⋅(H₂O)₁₈}_∞ (2) and {[Fe_xCu_yL₆]⋅(NO₃)₁₀⋅(H₂O)₁₈}_∞ (3; where x+y=5). Complexes with two-dimensional grid structures resulted from treatment with CoCl₂ or Cd(NO₃)₂ with L in complexes {[CoLCl₂]⋅DMF}_∞ (4) and {CdL(NO₃)₂}_∞ (5).

Synthesis and Methane-Binding Properties of Disulfide-Linked Cryptophane-0.0.0

Co-reporter:Marc A. Little;Jessica Donkin;Dr. Julie Fisher; Malcolm A. Halcrow;Jordan Loder ;Dr. Michaele J. Hardie

Angewandte Chemie 2012 Volume 124( Issue 3) pp:788-790

Publication Date(Web):

DOI:10.1002/ange.201106512

A Chiral, Self-Catenating and Porous MetalOrganic Framework and its Post-Synthetic Metal Uptake

Co-reporter:Dr. Tia Jacobs;Rob Clowes; Andrew I. Cooper;Dr. Michaele J. Hardie

Angewandte Chemie 2012 Volume 124( Issue 21) pp:5282-5285

Publication Date(Web):

DOI:10.1002/ange.201200758

M3L2 metallo-cryptophanes: [2]catenane and simple cages

Co-reporter:James J. Henkelis, Tanya K. Ronson, Lindsay P. Harding and Michaele J. Hardie

Chemical Communications 2011 vol. 47(Issue 23) pp:6560-6562

Publication Date(Web):13 May 2011

DOI:10.1039/C1CC10806A

Crystalline M3L2 complexes with either single cage or triply interlocking [2]catenane chiral structures are formed the self-assembly of host-like ligands with transition metals.

Bow-tie metallo-cryptophanes from a carboxylate derived cavitand

Co-reporter:Tanya K. Ronson, Harriott Nowell, Aleema Westcott and Michaele J. Hardie

Chemical Communications 2011 vol. 47(Issue 1) pp:176-178

Publication Date(Web):23 Jun 2010

DOI:10.1039/C0CC01284J

A new carboxylic acid functionalised cavitand forms [Cu3L2] metallo-cryptophanes with Cu(OAc)2 that can be linked together into dimers with the bridging ligand 1,2-bis(4-pyridyl)ethylene. Reaction of the cavitand with Co(OAc)2 gives a metallo-cryptophane with a central Co7 cluster.

New coordination polymers with extended arm cyclotriguaiacyclene ligands: 1D chains, and interpenetrating or polycatenating 2D (42.62)(4.62)2 networks

Co-reporter:Marc A. Little, Tanya K. Ronson and Michaele J. Hardie

Dalton Transactions 2011 vol. 40(Issue 45) pp:12217-12227

Publication Date(Web):25 Aug 2011

DOI:10.1039/C1DT10662G

A series of new 1D chain and 2D coordination polymers with cyclotriguaiacylene-type ligands are reported. A zig-zag 1D coordination chain is found in complex [Cd2(4ph4py)(NO3)3(H2O)2(DMA)2]·(NO3)·(DMA)4, where 4ph4py = tris[4-(4-pyridyl)benzoyl]-cyclotriguaiacylene and DMA = dimethylacetamide, while complex [Zn(4ph4py)2(CF3COO)(H2O)]·(CF3COO)(NMP)7, where NMP = N-methylpyrrolidone, has a doubly bridged coordination chain structure. Complexes [M(3ph3py)(NO3)2]·(NMP)4 where M = Co or Zn, 3ph3py = tris[3-(3-pyridyl)benzoyl]cyclotriguaiacylene, are isostructural and feature 1D ladder coordination chains. Complexes [Cd2(4ph4py)2(NO3)4(NMP)]·(NMP)9(H2O)4 and [Co(4ph4py)(H2O)2]·(NO3)2·(DMF)2, where DMF = dimethylformamide, both have (3,4)-connected 2D coordination polymers with a rare (42.62)(4.62)2 topology. A 2D coordination polymer with this topology is also found in complex [Co2(3ph4py)2(NO3)(H2O)5]·(NO3)3·(DMF)9 where 3ph4py = tris[3-(4-pyridyl)benzoyl]cyclotriguaiacylene. All 2D coordination polymer complexes are interpenetrating or polycatenating. [Co2(3ph4py)2(NO3)(H2O)5]3+ polymers form a 2D→3D polycatenation showing self-complementary “hand-shake” interactions between the host-type ligands.

Self-Assembled Cages with Cyclotriveratrylene-Type Host Molecules

Co-reporter:Michaele J. Hardie

Israel Journal of Chemistry 2011 Volume 51( Issue 7) pp:807-816

Publication Date(Web):

DOI:10.1002/ijch.201100060

Abstract

Cyclotriveratrylene (CTV) and related C₃-symmetric hosts are host molecules with a pyramidal shape and electron-rich molecular cavities. Appropriately functionalized CTV derivatives can self-assemble into nano- scale cage-like assemblies through metal–ligand interactions or hydrogen bonding. Examples of such assemblies include metallo-cryptophanes and hydrogen bonded capsules, M₄L₄ and M₄L₆ tetrahedra, M₆L₈ stella octangulas, along with cages with unusual topological features.

Recent advances in the chemistry of cyclotriveratrylene

Co-reporter:Michaele J. Hardie

Chemical Society Reviews 2010 vol. 39(Issue 2) pp:516-527

Publication Date(Web):07 Oct 2009

DOI:10.1039/B821019P

New chemistry of the cyclic molecular host cyclotriveratrylene (CTV) includes applications such as in sensors and separations; in self-organised materials such as gels, liquid crystals, dendritic systems, and self-assembled monolayers; and in metallo-supramolecular chemistry. This tutorial review covers aspects of CTV chemistry interest to supramolecular, coordination and host–guest chemists as well as those interested in self-organised systems.

Tripodal 4-Pyridyl-Derived Host Ligands and Their Metallo-Supramolecular Chemistry: Stella Octangula and Bowl-Shaped Assemblies

Co-reporter:Tanya K. Ronson ; Christopher Carruthers ; Julie Fisher ; Thierry Brotin ; Lindsay P. Harding ; Pierre J. Rizkallah

Inorganic Chemistry 2010 Volume 49(Issue 2) pp:675-685

Publication Date(Web):December 14, 2009

DOI:10.1021/ic901972h

The synthesis of five new cyclotriveratrylene derivatives with 4-pyridyl side arms is reported, along with the crystal structures of three of these. Three ligands with extended 4-pyridylphenyl side arms and a ligand derived from cyclotriphenolene have been shown to form [Pd6L8]12+ stella octangula assemblies using diffusion-ordered spectroscopy NMR and electrospray MS techniques. This confirms the generality of the stella octagula assembly, providing that the ligand arms show a degree of rigidity. The more flexible ether-linked ligand tris(4-pyridylmethyl)cyclotriguaiacylene forms a smaller [Pd3L4]6+ bowl-shaped assembly in the solid state and in solution. The previously reported ligand tris(4-pyridylmethylamino)cyclotriguaiacylene forms a similar assembly in solution.

Ag(I) Organometallic Coordination Polymers and Capsule with Tris-Allyl Cyclotriveratrylene Derivatives

Co-reporter:Marc A. Little ; Malcolm A. Halcrow ; Lindsay P. Harding

Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9486-9496

Publication Date(Web):September 23, 2010

DOI:10.1021/ic101211n

Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including η2-allyl, aryl, and OR groups binding to Ag(I). AgSbF6 gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag2L2 capsule dependent on reaction stoichiometry and reaction conditions. Isostructural coordination chain structures are found with AgBF4 and AgClO4, while use of Ag(CF3SO3) gives two-dimensional (2-D) and 3-D coordination polymers through bridging triflate anions.

Host–guest influence on metallo-supramolecular assemblies with a cyclotriveratrylene-type ligand

Co-reporter:Christopher Carruthers, Julie Fisher, Lindsay P. Harding and Michaele J. Hardie

Dalton Transactions 2010 vol. 39(Issue 2) pp:355-357

Publication Date(Web):08 Sep 2009

DOI:10.1039/B914285A

The structure-directing effect of guest binding in metallo-supramolecular assemblies of host-type ligands is observed with a 2-D coordination polymer formed between Cd(OAc)2 and tris(4-pyridylmethylamino)cyclotriguaiacylene in the presence of the globular guest o-carborane, and a trinuclear Cd(II) complex formed in solution in the absence of the bulky guest.

Metallo-gels and organo-gels with tripodal cyclotriveratrylene-type and 1,3,5-substituted benzene-type ligands

Co-reporter:Aleema Westcott, Christopher J. Sumby, Richard D. Walshaw and Michaele J. Hardie

New Journal of Chemistry 2009 vol. 33(Issue 4) pp:902-912

Publication Date(Web):12 Feb 2009

DOI:10.1039/B819352E

The cyclotriveratrylene-type ligands tris(4-[4-methyl-2,2′-bipyridyl]methyl)cyclotriguaiacylene 1 and tris(isonicotinoyl)cyclotriguaiacylene 2 form metallo-gels with Cu(II) and Ag(I) (for 1 only), while tris(3-(3-pyridyl)-1-thiourea)cyclotriguaiacylene 3 is a low molecular weight gelator (LMWG) for 2,2,2-trifluoroethanol. Benzene-1,3,5-tricarboxylic acid tris(4-hydroxyquinoline) ester 4 is a LMWG for acetone, while 1,3,5-tris(2-quinoline-methoxyl)benzene 5 forms Cu(II) metallo-gels. All gels have fibrous structures and show different thermal behaviour. Aside from the hydrogen bonding organo-gel of 3, an important intermolecular interaction within these gels is likely to be π–π stacking interactions. Crystal structures of a geometric isomer of 4 and of a discrete [Ag2(5)2]2+ complex are also reported herein.

New Network Structures from Cu(II) Complexes of Chelating Ligands with Appended Hydrogen Bonding Sites

Co-reporter:Maria D. Stephenson, Timothy J. Prior and Michaele J. Hardie

Crystal Growth & Design 2008 Volume 8(Issue 2) pp:643

Publication Date(Web):December 1, 2007

DOI:10.1021/cg700820d

Complexes [Cu(phenpyzda)Cl2(H2O)]·H2O (1) and [Cu(phenpyzda)Br2(H2O)]·2H2O (2), where phenpyzda = pyrazino[2,3-f][1,10]phenanthroline-2,3-diamide, show similar molecular structures with square planar Cu(II). Each complex has a complicated three-dimensional (3D) hydrogen bonding network with 1 having an unusual 3,9-connectivity. Use of the corresponding carboxylic acid, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarboxylic acid, results in the unexpected conversion of the ligand to 1H,3H-imidazol[2,3-f][1,10]phenanthroline (= imiphen) in the complex [CuCl3(imiphenH)]·2H2O, which has a 3D hydrogen bonded network structure of 3,6-connectivity. The more extended phenanthroline-based ligand 1,10-phenanthroline-5,6-[pteridine-2,4-diamine] was also synthesized, but no crystalline complexes of it were isolated. [Cu(bpy4diol)2](NO3)2·H2O (4), where bpy4diol = 2,2′-bipyridine-4,4′-diol, shows a two-dimensional (2D) hydrogen bonded network with hexagonal topology. [Cu(bpy4da)(NO3)2] (5) where bpy4da = 2,2′-bipyridine-4,4′-diamine has a 3D 2-fold interpenetrating α-Po related hydrogen bonded structure. Complexes [Cu(bpy4da)Cl2] (6) and [Cu(bpy5dmol)Cl2] (7) where bpy5dmol = 2,2′-bipyridine-5,5′-bis(hydroxymethyl) have similar chloro bridged coordination chains that hydrogen bond together into 3D and 2D networks, respectively. Despite their different hydrogen bonding patterns, complexes 6 and 7 are isomorphic.

The Dimeric Hand-Shake Motif in Complexes and MetalloSupramolecular Assemblies of Cyclotriveratrylene-Based Ligands

Co-reporter:Christopher Carruthers;TanyaK. Ronson Dr.;ChristopherJ. Sumby Dr.;Aleema Westcott Dr.;LindsayP. Harding Dr.;TimothyJ. Prior Dr.;Pierre Rizkallah Dr.;MichaeleJ. Hardie Dr.

Chemistry - A European Journal 2008 Volume 14( Issue 33) pp:10286-10296

Publication Date(Web):

DOI:10.1002/chem.200801264

Abstract

A series of clathrate and metal complexes with cyclotriveratrylene-like molecular host ligands show a similar dimeric homomeric inclusion motif in which a ligand arm of one host is the intra-cavity guest of another and vice versa. This “hand-shake” motif is found in the trinuclear transition metal complex [Cu₃Cl₆(1)]⋅CH₃CN⋅1.5 H₂O in which 1 is tris(4-[2,2′,6′,2′′-terpyridyl]benzyl)cyclotriguaiacylene; in the self-included M₄L₄ tetrahedral metallo-supramolecular assembly [Ag₄(2)₄] ⋅(BF₄)₄ in which 2 is tris-(2-quinolylmethyl)cyclotriguaiacylene; in the 1D coordination chains [Ag(4)]⋅ReO₄⋅CH₃CN and [Ag(5)]⋅SbF₆⋅3 DMF⋅H₂O in which 4 is tris(1H-imidazol-1-yl)cyclotriguaiacylene and 5 is tris{4-(2-pyridyl)benzyl}cyclotriguaiacylene; and in the acetone clathrate of tris{4-(2-pyridyl)benzyl-amino}cyclotriguaiacylene. Clathrates of ligands 2 and 5 do not show the same dimeric motif, although 2 has an extended homomeric inclusion motif that gives a hexagonal network.

Star-Burst Prisms with Cyclotriveratrylene-Type Ligands: A [Pd6L8]12+ Stella Octangular Structure

Co-reporter:Tanya K. Ronson Dr.;Julie Fisher Dr.;Lindsay P. Harding Dr.;Michaele J. Hardie Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 47) pp:

Publication Date(Web):24 OCT 2007

DOI:10.1002/anie.200703903

Star treatment: Host molecule tris(isonicotinoyl)cyclotriguaiacylene self-assembles with Pd(NO₃)₂ to form a [Pd₆L₈]¹²⁺ metallo-supramolecular cage of over 3 nm in diameter that resembles a stella octangular structure (see picture). ESMS and DOSY NMR studies show the assembly also exists in solution with a hydrodynamic radius of approximately 19 Å.

Star-Burst Prisms with Cyclotriveratrylene-Type Ligands: A [Pd6L8]12+ Stella Octangular Structure

Co-reporter:Tanya K. Ronson Dr.;Julie Fisher Dr.;Lindsay P. Harding Dr.;Michaele J. Hardie Dr.

Angewandte Chemie 2007 Volume 119(Issue 47) pp:

Publication Date(Web):24 OCT 2007

DOI:10.1002/ange.200703903

Fast sternförmig: Tris(isonicotinoyl)cyclotriguaiacylen bildet mit Pd(NO₃)₂ metallosupramolekulare [Pd₆L₈]¹²⁺-Käfigverbindungen mit einem Durchmesser über 3 nm (siehe Bild). ESMS- und DOSY-NMR-Studien belegen, dass die achteckige Struktur mit einem hydrodynamischen Radius um 19 Å auch in Lösung vorliegt.

The use of carborane anions in coordination polymers and extended solids

Co-reporter:Michaele J. Hardie

Journal of Chemical Crystallography 2007 Volume 37( Issue 1) pp:69-80

Publication Date(Web):2007 January

DOI:10.1007/s10870-006-9153-x

The use of carboranes as counter-anions for metal-organic frameworks or coordination polymers is reviewed. While carboranes are weakly coordinating they can form interactions to Ag(I) as well as other metal centers. Thus carboranes may have one of a number of roles in transition metal networks: as a non-coordinating templating counter-anion; as a bulky terminal ligand, and thus topologically trivial but likely to be structure-directing to some degree; or as a bridging ligand.

Coordination and hydrogen bonded network structures of Cu(II) with mixed ligands: a hybrid hydrogen bonded material, an infinite sandwich arrangement, and a 3-D net

Co-reporter:Maria D. Stephenson and Michaele J. Hardie

Dalton Transactions 2006 (Issue 28) pp:3407-3417

Publication Date(Web):11 Apr 2006

DOI:10.1039/B600357E

Mixed-ligand Cu(II) complexes with deprotonated trimesic acid and phenanthroline-type ligands were synthesised by solvothermal methods to form 2-D infinite hexagonal hydrogen bonded structures with additional trimesic acid (H3tma) molecules. The complex [Cu(phendione)2(H2tma)2]·2(H3tma)·1.65(CF3CH2OH)·2.5(H2O), where phendione = 1,10-phenanthroline-5,6-dione, has hydrogen bonded networks of [Cu(phendione)2(H2tma)2] complexes interspersed with layers of H3tma with a topologically identical hydrogen bonding network. Whereas in [Cu(1,10-phenanthroline)(H2tma)2]2·2(H3tma), a dimeric Cu(II) complex hydrogen bonds directly to additional H3tma molecules to form a three-layered 2-D network resembling an infinite sandwich. The synthesis and structures of simple Cu(II) complexes of the phendione ligand are also reported. One of these, [Cu(phendione)2Br2] shows a particularly polar packing arrangement.

Crystal-packing motifs of [Ag4L4]4+ star-burst tetrahedra

Co-reporter:Christopher J. Sumby, Michael J. Carr, Andreas Franken, John D. Kennedy, Colin A. Kilner and Michaele J. Hardie

New Journal of Chemistry 2006 vol. 30(Issue 10) pp:1390-1396

Publication Date(Web):24 Aug 2006

DOI:10.1039/B609356F

Further examples of a metallo-supramolecular ‘star-burst’ tetrahedron are reported from reaction of the ligand tris(4-pyridylmethylamino)cyclotriguaiacylene, 1, and AgPF6 in the presence of dinitrile species, or from reaction of 1 with Ag[1-Ph-closo-1-CB9H8-6-I]. Complex [Ag4(1)4(CH3CN)3]·4(PF6)·5(CH3CN)·(H2O) has a hexagonal structure where packing of the [Ag4(1)4]4+ tetrahedra mimics the close-packing of spheres. In complex {Ag4(1)4(CH3CN)2[PhCB9H8I]2}·2[PhCB9H8I]·11(CH3CN) the [1-Ph-closo-1-CB9H8-6-I]− anion coordinates to the [Ag4(1)4]4+ tetrahedron through Ag–I and Ag⋯H–B interactions, and a less symmetric packing motif is found. The synthesis and crystal structure of the novel monocarbaborane species (NEt4)[1-Ph-closo-1-CB9H8-6-I] are also reported.

Tris(pyridylmethylamino)cyclotriguaiacylene Cavitands: An Investigation of the Solution and Solid-State Behaviour of Metallo-Supramolecular Cages and Cavitand-Based Coordination Polymers

Co-reporter:Christopher J. Sumby Dr.;Julie Fisher Dr.;Timothy J. Prior Dr. Dr.

Chemistry - A European Journal 2006 Volume 12(Issue 11) pp:

Publication Date(Web):21 FEB 2006

DOI:10.1002/chem.200501542

The synthesis of the three isomeric tris(pyridylmethylamino)cyclotriguaiacylene cavitands is reported, along with the crystal structures of the 2- and 4-pyridyl derivatives. The generality of a previously described [Ag₂{tris(3-pyridylmethylamino)cyclotriguaiacylene}₂]²⁺ dimeric capsule motif and the [Ag₄{tris(4-pyridylmethylamino)cyclotriguaiacylene}₄]⁴⁺ tetrahedron with several silver salts was confirmed in the solid state and the corresponding solution species were investigated by NMR spectroscopy. Host–guest interactions in these systems have been probed and these interactions are demonstrated to alter and influence the self-assembly outcome of the reaction. Notably, introduction of larger glutaronitrile guest molecules to the [Ag₄L₄]⁴⁺ tetrahedron system prevents formation of the tetrahedral structure, resulting instead in the formation of a 4.8² coordination network in the solid state. In the absence of templating acetonitrile guests in the [Ag₂(3)₂]²⁺ capsule system, formation of a cage-based one-dimensional coordination polymer is observed.

Network structures of cyclotriveratrylene and its derivatives

Co-reporter:Michaele J. Hardie, Ruksanna Ahmad and Christopher J. Sumby

New Journal of Chemistry 2005 vol. 29(Issue 10) pp:1231-1240

Publication Date(Web):27 Jul 2005

DOI:10.1039/B505579B

The host molecule cyclotriveratrylene can be incorporated into network structures by acting as a hydrogen bond acceptor or as a chelating ligand for Group 1 metals. New CTV-based ligands with pyridyl functional groups have been synthesised for use as multifunctional ligands in coordination networks. Resultant hydrogen bonded network structures and coordination networks show a range of chain, 2-D and 3-D structures with hexagonal 63 nets predominating. Recent results are discussed including highly complex 3-D networks where the molecular hosts pack in a tetrameric back-to-back fashion.

Capsules and Star-Burst Polyhedra: An [Ag2L2] Capsule and a Tetrahedral [Ag4L4] Metallosupramolecular Prism with Cyclotriveratrylene-Type Ligands

Co-reporter:Christopher J. Sumby Dr. Dr.

Angewandte Chemie 2005 Volume 117(Issue 39) pp:

Publication Date(Web):7 SEP 2005

DOI:10.1002/ange.200501358

Ein flexibler Wirt: Pyridylsubstituierte Cyclotriveratrylenliganden in Verbindung mit geometrisch passenden Silberzentren führten zur Isolierung und strukturellen Charakterisierung einer kompakten molekularen [M₂L₂]-Kapsel und eines tetraedrischen [M₄L₄]-Prismas (siehe Struktur). In der Kapsel sind zwei koordinierte CH₃CN-Moleküle eingeschlossen, während das Prisma eine ungewöhnliche Starburst-Form hat und ebenfalls als Wirt für CH₃CN-Moleküle fungiert.

Capsules and Star-Burst Polyhedra: An [Ag2L2] Capsule and a Tetrahedral [Ag4L4] Metallosupramolecular Prism with Cyclotriveratrylene-Type Ligands

Co-reporter:Christopher J. Sumby,Michaele J. Hardie

Angewandte Chemie International Edition 2005 44(39) pp:6395-6399

Publication Date(Web):

DOI:10.1002/anie.200501358

Building blocks for cyclotriveratrylene-based coordination networks

Co-reporter:Michaele J. Hardie, Rachael M. Mills and Christopher J. Sumby

Organic & Biomolecular Chemistry 2004 vol. 2(Issue 20) pp:2958-2964

Publication Date(Web):17 Sep 2004

DOI:10.1039/B407165D

The incorporation of three-fold symmetric organic host molecules into coordination polymers should allow for the construction of new and interesting network structures, capable of multiple inclusion behaviour. A range of new multi-dentate bridging ligands/molecular hosts have been prepared by appending nitrogen-containing heterocycles to either cyclotricatechylene, or cyclotriguaiacylene cores. These compounds were obtained in a single-step reaction from readily available precursors, with moderate to good yields, and characterised by a combination of NMR spectroscopy, mass spectrometry and elemental analysis. Two of the new compounds were characterised by X-ray crystallography, revealing different modes of self inclusion behaviour, which indicate the potential importance of π-donor stabilisation by CTV derivatives in host–guest chemistry.

A bis(disulfide)-linked offset cryptophane

Co-reporter:Marc A. Little, Malcolm A. Halcrow and Michaele J. Hardie

Chemical Communications 2013 - vol. 49(Issue 15) pp:NaN1514-1514

Publication Date(Web):2013/01/17

DOI:10.1039/C3CC38768B

A new bis(disulfide)-linked offset dimer is formed from a dithiolated analogue of cyclotriguaiacylene. Unlike a similar tris(disulfide)-linked example, this is not a true cryptophane as the offset nature of the dimerisation and intramolecular host–guest interactions preclude its use as a host.

Host–guest influence on metallo-supramolecular assemblies with a cyclotriveratrylene-type ligand

Co-reporter:Christopher Carruthers, Julie Fisher, Lindsay P. Harding and Michaele J. Hardie

Dalton Transactions 2010 - vol. 39(Issue 2) pp:NaN357-357

Publication Date(Web):2009/09/08

DOI:10.1039/B914285A

The structure-directing effect of guest binding in metallo-supramolecular assemblies of host-type ligands is observed with a 2-D coordination polymer formed between Cd(OAc)2 and tris(4-pyridylmethylamino)cyclotriguaiacylene in the presence of the globular guest o-carborane, and a trinuclear Cd(II) complex formed in solution in the absence of the bulky guest.

New coordination polymers with extended arm cyclotriguaiacyclene ligands: 1D chains, and interpenetrating or polycatenating 2D (42.62)(4.62)2 networks

Co-reporter:Marc A. Little, Tanya K. Ronson and Michaele J. Hardie

Dalton Transactions 2011 - vol. 40(Issue 45) pp:NaN12227-12227

Publication Date(Web):2011/08/25

DOI:10.1039/C1DT10662G

A series of new 1D chain and 2D coordination polymers with cyclotriguaiacylene-type ligands are reported. A zig-zag 1D coordination chain is found in complex [Cd2(4ph4py)(NO3)3(H2O)2(DMA)2]·(NO3)·(DMA)4, where 4ph4py = tris[4-(4-pyridyl)benzoyl]-cyclotriguaiacylene and DMA = dimethylacetamide, while complex [Zn(4ph4py)2(CF3COO)(H2O)]·(CF3COO)(NMP)7, where NMP = N-methylpyrrolidone, has a doubly bridged coordination chain structure. Complexes [M(3ph3py)(NO3)2]·(NMP)4 where M = Co or Zn, 3ph3py = tris[3-(3-pyridyl)benzoyl]cyclotriguaiacylene, are isostructural and feature 1D ladder coordination chains. Complexes [Cd2(4ph4py)2(NO3)4(NMP)]·(NMP)9(H2O)4 and [Co(4ph4py)(H2O)2]·(NO3)2·(DMF)2, where DMF = dimethylformamide, both have (3,4)-connected 2D coordination polymers with a rare (42.62)(4.62)2 topology. A 2D coordination polymer with this topology is also found in complex [Co2(3ph4py)2(NO3)(H2O)5]·(NO3)3·(DMF)9 where 3ph4py = tris[3-(4-pyridyl)benzoyl]cyclotriguaiacylene. All 2D coordination polymer complexes are interpenetrating or polycatenating. [Co2(3ph4py)2(NO3)(H2O)5]3+ polymers form a 2D→3D polycatenation showing self-complementary “hand-shake” interactions between the host-type ligands.

Bow-tie metallo-cryptophanes from a carboxylate derived cavitand

Co-reporter:Tanya K. Ronson, Harriott Nowell, Aleema Westcott and Michaele J. Hardie

Chemical Communications 2011 - vol. 47(Issue 1) pp:NaN178-178

Publication Date(Web):2010/06/23

DOI:10.1039/C0CC01284J

A new carboxylic acid functionalised cavitand forms [Cu3L2] metallo-cryptophanes with Cu(OAc)2 that can be linked together into dimers with the bridging ligand 1,2-bis(4-pyridyl)ethylene. Reaction of the cavitand with Co(OAc)2 gives a metallo-cryptophane with a central Co7 cluster.

Controlling the assembly of cyclotriveratrylene-derived coordination cages

Co-reporter:James J. Henkelis and Michaele J. Hardie

Chemical Communications 2015 - vol. 51(Issue 60) pp:NaN11943-11943

Publication Date(Web):2015/06/10

DOI:10.1039/C5CC03071D

A review of the emerging field of cyclotriveratrylene-derived coordination cages is presented. Ligand-functionalised cyclotriveratrylene (CTV) derivatives self-assemble with a range of metal cations to afford coordination cages, polymers and topologically non-trivial constructs, such as [2]catenanes and a self-entangled cube. Increased control over their self-assembly allows for the controlled and predictable formation of well-defined coordination cages for application in host–guest and recognition chemistry, with surfactant binding and single-crystal-to-single-crystal (SCTSC) uptake of small-molecule guests being observed.

M3L2 metallo-cryptophanes: [2]catenane and simple cages

Co-reporter:James J. Henkelis, Tanya K. Ronson, Lindsay P. Harding and Michaele J. Hardie

Chemical Communications 2011 - vol. 47(Issue 23) pp:NaN6562-6562

Publication Date(Web):2011/05/13

DOI:10.1039/C1CC10806A

Crystalline M3L2 complexes with either single cage or triply interlocking [2]catenane chiral structures are formed the self-assembly of host-like ligands with transition metals.

Recent advances in the chemistry of cyclotriveratrylene

Co-reporter:Michaele J. Hardie

Chemical Society Reviews 2010 - vol. 39(Issue 2) pp:NaN527-527

Publication Date(Web):2009/10/07

DOI:10.1039/B821019P

New chemistry of the cyclic molecular host cyclotriveratrylene (CTV) includes applications such as in sensors and separations; in self-organised materials such as gels, liquid crystals, dendritic systems, and self-assembled monolayers; and in metallo-supramolecular chemistry. This tutorial review covers aspects of CTV chemistry interest to supramolecular, coordination and host–guest chemists as well as those interested in self-organised systems.

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies

Co-reporter:Flora L. Thorp-Greenwood, Tanya K. Ronson and Michaele J. Hardie

Chemical Science (2010-Present) 2015 - vol. 6(Issue 10) pp:NaN5792-5792

Publication Date(Web):2015/07/14

DOI:10.1039/C5SC01801C

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI4CuII1.5(L1)3(CN)6]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu3(L2)4(H2O)3]·6(OTf)·n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (43.123)(42.122) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII analogue [Cu2(L1)2(NMP)(H2O)]·4BF4·12NMP·1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.82 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C60 through soaking the crystals in a toluene solution.

M12L8 metallo-supramolecular cube with cyclotriguaiacylene-type ligand: spontaneous resolution of cube and its constituent host ligand

Co-reporter:Jonathan M. Fowler, Flora L. Thorp-Greenwood, Stuart L. Warriner, Charlotte E. Willans and Michaele J. Hardie

Chemical Communications 2016 - vol. 52(Issue 56) pp:NaN8702-8702

Publication Date(Web):2016/06/22

DOI:10.1039/C6CC04130B

The racemic ligand (±)-tris-(4-methylthiazolyl)cyclotriguaiacylene forms a homochiral crystalline Ag12L8 cube with spontaneous resolution. The ligand itself likewise crystallises in a chirally pure fashion in two clathrate complexes. Ag12L8 is the first example of a cyclotriguaiacylene-type coordination cube and a rare example of a M12L8-type metallo-cube.