21 research outputs found
Metallo-cryptophane cages from cis-linked and trans-linked strategies.
Data supporting study of Pd(II) metallo-cage species from cyclotriguaiacylene derived ligands
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Energy and Electron Transfer Dynamics within a Series of Perylene Diimide/Cyclophane Systems.
Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state.S.T.J.R. thanks the Cambridge Home and European Scholarship Scheme and the Robert Gardiner memorial scholarship. S.T.J.R., A.F. and O.A.S. thank the ERC starting investigator grant ASPiRe (project no. 240629) and the EPSRC (reference no. EP/G060649/1). Femtosecond and nanosecond spectroscopy (R.M.Y.), EPR spectroscopy (M.D.K.) and phosphorescence spectroscopy (Y.W.) were supported as part of the ANSER Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. DE-SC0001059. J.F.S., J.J.H., N.H., N.A.V. and E.D.J. acknowledge the Joint Center of Excellence in Integrated Nano-Systems (JCIN) between KACST and Northwestern University (Project 34-946) for their continued financial support. E.J.D. acknowledges NSF and Ryan fellowships. A.H. and W.M.N. thank the COST Action CM1005 “Supramolecular Chemistry in Water” and the DFG (grant NA-686/5) for financial support.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/jacs.5b1032
Controlling the assembly of cyclotriveratrylene-derived coordination cages
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
Tuning the coordination chemistry of cyclotriveratrylene ligand pairs through alkyl chain aggregation
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(C2B 9H11)2]](DMF)}∞ (complex 1p), and a 2D sheet of 4·82 topology in {[Cd(L1p)(ONO 2)2(H2O)]·(DMF)·0.5(Et 2O)}∞ (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(C2B9H 11)2]2·1.5(MeNO2)} ∞ (complex 3p) and a novel, compressed octahedral structure with palladium(ii) cations, [Pd6(L2p)4(CF 3CO2)12] (complex 4p). Neither complex was accessible with the methylated congener tris(2-quinolylmethyl)- cyclotriguaiacylene (L2m)
Metallo-cryptophanes decorated with Bis-N-heterocyclic carbene ligands: self-assembly and guest uptake into a nonporous crystalline lattice
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
M3L2 metallo-cryptophanes: [2]catenane and simple cages
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
Coordination Polymers Utilizing <i>N</i>‑Oxide Functionalized Host Ligands
Pyridyl functionalized host molecules are oxidized to
their <i>N</i>-oxide analogues and form a series of coordination
polymers
and discrete complexes with transition metal cations. Complex {[Ag<sub>3</sub>(NMP)<sub>6</sub>(L1)<sub>2</sub>]·3(ClO<sub>4</sub>)}<sub>∞</sub> where L1 = tris(isonicotinoyl-<i>N</i>-oxide)cyclotriguaiacylene,
NMP = <i>N</i>-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)<sub>2</sub>]<sup>2+</sup> where M = Zn, Cd, Cu. Ligand L2 = tris(nicotinoyl-<i>N</i>-oxide)cyclotriguaiacylene forms a 2-D coordination polymer
with 4<sup>4</sup> (sql) grid topology in complexes {[M(L2)<sub>2</sub>(DMF)<sub>2</sub>]·2ClO<sub>4</sub>·8(DMF)}<sub>∞</sub> M = Cd or Cu, DMF = <i>N,N</i>′-dimethylformamide,
and a double-linked chain structure in {[Co(L2)<sub>2</sub>(DMF)<sub>2</sub>]·2NO<sub>3</sub>·4(DMF)·H<sub>2</sub>O}<sub>∞</sub>, and both types of structure feature hand-shake self-inclusion
motifs either within or between the polymers. 2-D coordination networks
with 6<sup>3</sup> (hcb) topologies are found in complexes {[M(L3)(NO<sub>3</sub>)<sub>2</sub>]·2(DMF)}<sub>∞</sub> (M = Cd, Zn)
and {[Cu<sub>5</sub>(L3)<sub>2</sub>Cl<sub>10</sub>(NMP)<sub>4</sub>]}<sub>∞</sub> where L3 = tris(2-pyridylmethyl)cyclotriguaiacylene,
while [Ag<sub>2</sub>(L3)<sub>2</sub>(NMP)<sub>4</sub>]·2(BF<sub>4</sub>)·2(NMP) has a discrete dimeric structure which again
shows hand-shake host–guest interactions supported by π–π
stacking
Coordination Polymers Utilizing <i>N</i>‑Oxide Functionalized Host Ligands
Pyridyl functionalized host molecules are oxidized to
their <i>N</i>-oxide analogues and form a series of coordination
polymers
and discrete complexes with transition metal cations. Complex {[Ag<sub>3</sub>(NMP)<sub>6</sub>(L1)<sub>2</sub>]·3(ClO<sub>4</sub>)}<sub>∞</sub> where L1 = tris(isonicotinoyl-<i>N</i>-oxide)cyclotriguaiacylene,
NMP = <i>N</i>-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)<sub>2</sub>]<sup>2+</sup> where M = Zn, Cd, Cu. Ligand L2 = tris(nicotinoyl-<i>N</i>-oxide)cyclotriguaiacylene forms a 2-D coordination polymer
with 4<sup>4</sup> (sql) grid topology in complexes {[M(L2)<sub>2</sub>(DMF)<sub>2</sub>]·2ClO<sub>4</sub>·8(DMF)}<sub>∞</sub> M = Cd or Cu, DMF = <i>N,N</i>′-dimethylformamide,
and a double-linked chain structure in {[Co(L2)<sub>2</sub>(DMF)<sub>2</sub>]·2NO<sub>3</sub>·4(DMF)·H<sub>2</sub>O}<sub>∞</sub>, and both types of structure feature hand-shake self-inclusion
motifs either within or between the polymers. 2-D coordination networks
with 6<sup>3</sup> (hcb) topologies are found in complexes {[M(L3)(NO<sub>3</sub>)<sub>2</sub>]·2(DMF)}<sub>∞</sub> (M = Cd, Zn)
and {[Cu<sub>5</sub>(L3)<sub>2</sub>Cl<sub>10</sub>(NMP)<sub>4</sub>]}<sub>∞</sub> where L3 = tris(2-pyridylmethyl)cyclotriguaiacylene,
while [Ag<sub>2</sub>(L3)<sub>2</sub>(NMP)<sub>4</sub>]·2(BF<sub>4</sub>)·2(NMP) has a discrete dimeric structure which again
shows hand-shake host–guest interactions supported by π–π
stacking