Leigh F. Jones

Upon metal coordination, the upper rim modification of the Schiff base ligand 2-methoxy-6-((methylimino)methyl)phenol gives rise to a new family of [M(II)₇] (M = Co, Ni, Zn) pseudo metallocalix[6]arenes in the form of [Co(II)₇(OMe)₆(L₃)₆](NO₃)₂·2H₂O·3MeOH (1), [Ni(II)₇(OMe)₆(L₃)₆](NO₃)₂·2H₂O (4), [Zn(II)₇(OH)₂(OMe)₄(L₃)₆](NO₃)₂·10H₂O·4MeOH (5) and [Zn(II)₇(OMe)₆(L₄)₆](NO₃)₂·13H₂O·10MeOH (6), where L₃H = 2-methoxy-4-phenyl-6-[(methylimino)methyl]phenol and L₄H = 2-methoxy-4-tolyl-6-[(methylimino)methyl]phenol. The upper rim functionalisation provides this family with extensions to their molecular cavity walls when compared to their previously reported siblings. Attempts at encapsulating guest moieties (e.g., C₆₀) unexpectedly give rise to the dimeric complex [Co(II)Co(III)(L₃)₃(NO₃)₂]·H₂O (3).

Upon metal coordination, the upper rim modification of the Schiff base ligand 2-methoxy-6-((methylimino)methyl)phenol gives rise to a new family of [M(II)₇] (M = Co, Ni, Zn) pseudo metallocalix[6]arenes in the form of [Co(II)₇(OMe)₆(L₃)₆](NO₃)₂^.H₂O^.3MeOH (1), [Ni(II)₇(OMe)₆(L₃)₆](NO₃)₂^.2H₂O (4), [Zn(II)₇(OH)₂(OMe)₄(L₃)₆](NO₃)₂^.4MeOH^.10H₂O (5) and [Zn(II)₇(OMe)₆(L₄)₆](NO₃)₂^.10MeOH^.13H₂O (6), where L₃H = 2-methoxy-4-phenyl-6-[(methylimino)methyl]phenol and L₄H = 2-methoxy-4-tolyl-6-[(methylimino)methyl]phenol). The upper rim functionalisation provides this family with extensions to their molecular cavity walls when compared to their previously reported siblings. Attempts at encapsulating guest moieties (e.g. C₆₀) unexpectedly give rise to the monometallic complex [Co(II)Co(III)(L₃)₃(NO₃)₂]^.H₂O (3).

We present the encapsulation of a number of small organic guest moieties within the molecular cavities of pseudo [M ₇ ] (M = Co( ii ), Ni( ii ) and Zn( ii )) metallocalix[6]arene hosts.

A series of nickel (II) bis-phosphine organometallic complexes along with two pseudo [M₇] (M = Ni(II), Zn(II)) metallocalix[6]arene complexes and a dysprosium acetate coordination polymer have each been crystallised in the presence of localized magnetic fields set up using neodymium magnets, using custom made Magnetic Crystallization Towers (MCTs). In all cases, whether the product complex is diamagnetic or paramagnetic, a complex spatial patterning of the crystals occurs based on the orientation of the magnetic field lines. When using magnetic block towers, the crystallization generally occurs adjacent to the magnet face. The effects of nucleation and solution concentration gradients on the crystallization process are also explored. These observations show how the crystallization process is affected by magnetic fields and thus these results have far-reaching effects which most certainly will include crystallization and ion migrations in biology.

The crystallization of nickel (II) bis-phosphine and nickel and zinc cluster complexes have been carried out in localized magnetic fields set up using neodymium magnets, including custom made Magnetic Crystallization Towers (MCTs). In all cases, whether the product complex is diamagnetic or paramagnetic, a complex spatial patterning of the crystals occurs based on the orientation of the magnetic field lines. The effects of nucleation, and solution concentration gradients on the crystallization process are also explored. These observations therefore show how the crystallization process is affected by magnetic fields and thus these results have far-reaching effects which most certainly will include crystallization and ion migrations in biology.

N-alkylated C₂-symmetric amino acid amide derivatives were shown to catalyse the Michael addition of 2-hydroxy-1,4-napthoquinone to β-nitrostyrene, achieving a maximum ee of 44%. The corresponding trifluoroacetic acid salts also catalysed the aldol reaction between 4-nitrobenzaldehyde and hydroxyacetone, leading to the formation of predominantly syn-aldol products in up to 55% ee. Aspects of the solvent dependence of the aldol reaction and the H-bonding of the catalyst were investigated.

The novel multitopic ligands N-hydroxy-4-((2-hydroxy-3-methoxybenzyl)amino)benzamide (L₃H₃) and N-hydroxy-4-((2-hydroxybenzyl)amino)benzamide (L₄H₃) have been synthesised through the Schiff base coupling and subsequent reduction of 4-aminophenylhydroxamic acid and either o-vanillin (to give L₃H₃) or 2-hydroxybenzaldehyde (to give L₄H₃). These linear multitopic ligands bind Cu(II) centres at both the hydroxamate and phenol ends to form the 1-D coordination polymers [Cu(II)(L₃H₂)₂]_n (1) and {[Cu(II)(L₄H₂)₂]·2MeOH}_n (2). Slight differences in the structures of L₃H₃ and L₄H₃ lead to significant extended connectivity changes upon Cu(II) metalation that are exampled by a 27% decrease in intra-chain Cu(II)⋯Cu(II) distance upon moving from 1 to 2. The significant conformation and metal binding differences shown by L₃H₂ ⁻ and L₄H₂ ⁻ in 1 and 2 respectively have been rationalised using density functional theory (DFT) calculations. Hirshfeld surface analysis has been employed to assess and visualise the intra- and intermolecular interactions in both complexes.