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Jack M. Harrowfield 고신대학교 자연과학연구소 2008 고신대학교 자연과학연구소 논문집 Vol.15 No.-
The work described above is no more than a fragment of contemporary chemistry illustrating some steps in its evolution. The ability to form grids from appropriately designed ligands, for example, has led to syntheses using functionalised ligands which provide larger, spatially oriented arrays of the functional groups [25] with the potential for selective interactions with other molecules, thus leading to even larger aggregates which may be of importance in catalysis, analysis or even medical therapy [28,30). There is a need for new methods to detect and quantify weak interactions between chemical species [31], driven by the increasing complexity of the systems studied, and their development should lead to even greater sophistication of synthetic systems [32], some of which may even challenge the efficacy of Nature in ensuring the survival of mankind.
Lee, Young Hoon,Harrowfield, Jack M.,Kim, Jong Seung,Kim, Yang,Lee, Min Hee,Lim, Woo Taik,Park, Yu Cheol,Thué,ry, Pierre Royal Society of Chemistry 2009 Dalton Transactions Vol.2009 No.3
<P>Selective functionalisation of the tridentate ligand 1-(2-aminoethyl)-3-methyl-3-(2-pyridyl)azetidine at its terminal amino-nitrogen atom can be readily achieved by both reductive alkylation and simple alkylation reactions to give tri-, quadri-, quinque- and sexi-dentate derivatives. Simple alkylation by 2-picolinyl chloride provides the only example of a second reaction pathway where the azetidine ring of the reactant has undergone activation towards ring opening. Structural characterisation of the Cu(<SMALL>II</SMALL>) complexes of these ligands has revealed several remarkable aspects of their solid-state coordination chemistry, including the formation of infinite helical aggregates through π-stacking and tetramerisation through carboxylate bridging, as well as further examples of the crystallisation of mixed species found to be rather common with complexes of the parent ligand.</P> <P>Graphic Abstract</P><P>Elaboration of a pyridyl–azetidine to obtain ligands of higher denticity enables the formation of a variety of Cu(<SMALL>II</SMALL>) complexes showing unusual solid state structures. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b812298a'> </P>
Supramolecular Interactions of Terpyridine-Derived Cores of Metallomesogen Precursors
Lee, Young Hoon,Harrowfield, Jack M.,Shin, Jong Won,Won, Mi Seon,Rukmini, Elisabeth,Hayami, Shinya,Min, Kil Sik,Kim, Yang Molecular Diversity Preservation International (MD 2013 INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES Vol.14 No.10
<P>Use of Hirshfeld surfaces calculated from crystal structure determinations on various transition metal ion complexes of three terpyridine ligands carrying trimethoxyphenyl substituents has enabled an assessment of the contribution made by the ligand components to the interactions determining the lattice structures, interactions expected also to be present in metallomesogens derived from similar ligands. The form of the link joining the trimethoxyphenyl substituent to the 4′ position of 2,2′;6′,2″-terpyridine is of some importance. In the case of the Co(II) complexes of two of the ligands, their spin-crossover characteristics can be rationalised in terms of the different interactions seen in their lattices.</P>
Some post-Wernerian coordination chemistry
Cho, J.H.,Harrowfield, J.,Kim, J.Y.,Kim, Y.,Lee, Y.H.,Ohto, K.,Thuery, P.,Won, M.S.,Woo, A. Pergamon Press 2013 Polyhedron Vol.52 No.-
The crystal structures of one inert and six labile metal ion complexes have been analysed as a means of illustrating the refinements that X-ray crystallography has brought to the understanding of coordination chemistry so profoundly influenced by Alfred Werner. Contemporary interest in various weak interactions evident from structural studies can be related to the Wernerian concepts of <<haupt→> and <<neben-valenz>>.
Functionalised azetidines as ligands: pyridyl-complemented coordination
Lee, Young Hoon,Harrowfield, Jack,Kim, Yang,Lim, Woo Taik,Park, Yu Cheol,Thué,ry, Pierre Royal Society of Chemistry 2009 Dalton Transactions Vol.2009 No.3
<P>A relatively simple azetidine derivative with 2-aminoethyl and 2-pyridyl substituents functions as a tridentate ligand towards Cu(<SMALL>II</SMALL>), giving species in which the CuN<SUB>3</SUB> unit is essentially planar and that, in the solid state, show a subtle balance between mononuclear and binuclear forms, allowing both to be simultaneously present in some lattices. Displacement of the ligand from Cu(<SMALL>II</SMALL>) by the use of cyanide results in the formation of cyanogen, which appears to slowly react with the free amine to give an oxamidine characterised in its doubly-deprotonated form as its binuclear Ni(<SMALL>II</SMALL>) complex.</P> <P>Graphic Abstract</P><P>A tridentate pyridylazetidine derivative forms binuclear complexes with Cu(<SMALL>II</SMALL>) and terephthalate in which the dicarboxylate is present in two protonation states. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b812295d'> </P>
A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting
Bernhardt, Paul V.,Harrowfield, Jack M.,Kim, Yang,Lee, Young-Hoon,Park, Yu-Cheol,Sujandi, Sujandi Korean Chemical Society 2007 Bulletin of the Korean Chemical Society Vol.28 No.4
The conversion of both the racemic and resolved forms of the Co(III) complex of an hydroxymethyl-substituted tripodal hexamine to macrobicycles via reaction with formaldehyde and nitromethane (and subsequent reduction of the product) has been conducted. The prospect is that it will provide cage complexes in which the hydroxyl substituent is sufficiently remote from the metal ion centre for its nucelophilicity to be largely unaffected. X-ray structure determinations have been used to characterise these new cage species as well as some complexes of the precursor hexamine and its mono-aminal. The electrochemistry and optical activity of the complexes have also been studied in detail.
A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting
Paul V. Bernhardt,Jack M. Harrowfield,김양,이영훈,Yu Cheol Park,Sujandi 대한화학회 2007 Bulletin of the Korean Chemical Society Vol.28 No.4
The conversion of both the racemic and resolved forms of the Co(III) complex of an hydroxymethyl-substituted tripodal hexamine to macrobicycles via reaction with formaldehyde and nitromethane (and subsequent reduction of the product) has been conducted. The prospect is that it will provide cage complexes in which the hydroxyl substituent is sufficiently remote from the metal ion centre for its nucelophilicity to be largely unaffected. X-ray structure determinations have been used to characterise these new cage species as well as some complexes of the precursor hexamine and its mono-aminal. The electrochemistry and optical activity of the complexes have also been studied in detail.