Heterodimetallic germanium(IV) complex structures with transition metals

The hydrothermal synthesis and structural characterization of a number of complex compounds containing the divalent tris(oxalato-O,O¢)germanate anion, [Ge(C2O4)3]2-, or the neutral bis(oxalate-O,O¢)germanium fragment, [Ge(C2O4)2], with transition-metal (M) cationic complexes of 1,10¢-phenanthroline (phen) is reported: [M(phen)3]- [Ge(C2O4)3]âxH2O [where M2+ ) Cu2+ (1a and 1b), Fe2+ (2a and 2b), Ni2+ (3), Co2+ (4); x ) 0.2 for 2b], [MGe- (phen)2(í2-OH)2(C2O4)2] [where M2+ ) Cd2+ (5) and Cu2+ (6)]. The isolation of two polymorphs with Cu2+ (1a and 1b) and other pseudo-polymorphs for Fe2+ (2a and 2b) was rationalized based on slightly different molar ratios for the starting materials. All compounds have been characterized using EDS, SEM, vibrational spectroscopy (FT-IR and FT-Raman), thermogravimetry, and CHN elemental composition and their structure determined on the basis of single-crystal X-ray diffraction studies. The crystal packing of the different chemical moieties for each series of compounds was discussed on the basis of the various intermolecular interactions present (strong C-Hâââð and weak C-HâââO hydrogen-bonding interactions, C-Hâââð and ð-ð contacts).FCT - SFRH/BPD/9309/2002FCT - SFRH/BPD/14410/2003FEDERPOCI - 201

Homochiral self-sorted and emissive IrIII metallo-cryptophanes

We thank the EPSRC (DTG award 1238852, EP/K039202/1, EP/M02105X/1, EP/J001325/1), Leverhulme Trust (RPG-2014-148), University of St Andrews, and the MEXT/JSPS Grants in Aid for Scientific Research (JP25102005 and JP25102001) for funding; Simon Barrett for assistance with NMR; Martin Huscroft for assistance with HPLC, and Stephen Boyer for elemental analysis measurements.The racemic ligands (±)-tris(isonicotinoyl)-cyclotriguaiacylene (L1), or (±)-tris(4-pyridyl-methyl)-cyclotriguaiacylene (L2) assemblewith racemic (Λ, Δ)- [Ir(ppy)2(MeCN)2]+, in which ppy = 2-phenylpyridinato to form [{Ir(ppy)2}3(L)2]3+ metallo-cryptophane cages. The crystal structure of [{Ir(ppy)2}3(L1)2]∙3BF4 has MM-ΛΛΛ nd PP-ΔΔΔ isomers, and homochiral self-sorting occurs in solution, a processaccelerated by a chiral guest. Self-recognition between L1 and L2 within cagesdoes not occur, and cages show very slow ligand-exchange. Both cages are phosphorescent,with [{Ir(ppy)2}3(L2)2]3+ havingenhanced and blue-shifted emission when compared with [{Ir(ppy)2}3(L1)2]3+ .PostprintPeer reviewe

Metallo-cryptophane cages from cis-linked and trans-linked strategies.

Data supporting study of Pd(II) metallo-cage species from cyclotriguaiacylene derived ligands

An Area-Specific, International Community-Led Approach to Understanding and Addressing Equality, Diversity, and Inclusion Issues within Supramolecular Chemistry

Diversity, equality, and inclusion (DEI/EDI) are pressing issues in chemistry and the natural sciences. In this Essay we share how an area-specific approach is “calling in” the community so that it can act to address EDI issues, and support those who are marginalised. Women In Supramolecular Chemistry (WISC) is an international network that aims to support equality, diversity, and inclusion within supramolecular chemistry. WISC has taken a field-specific approach using qualitative research methods with scientists to identify the support that is needed and the problems the supramolecular community needs to address. Herein, we present survey data from the community which highlight the barriers that are faced by those who take career breaks for any reason, a common example is maternity leave, and the importance of mentoring to aid progression post-PhD. In conclusion, we set out an interdisciplinary and creative approach to addressing EDI issues within supramolecular chemistry

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