Metals, macrocycles and molecular assemblies – macrocyclic complexes in metallo-supramolecular chemistry

Lindoy, Leonard F.,Park, Ki-Min,Lee, Shim Sung The Royal Society of Chemistry 2013 Chemical Society reviews Vol.42 No.4

<P>In this <I>tutorial review</I> the use of macrocyclic complexes as building blocks in a selection of supramolecular systems is discussed with emphasis on the properties, such as enhanced stabilities, that cyclic ligands and their complexes may impart on the resulting assemblies. An aim of the review is to exemplify the versatility of macrocyclic ligand complexes for use as components in a range of both discrete and polymeric systems. The use of macrocyclic systems for controlling CuI aggregation, as scaffolds for metal-cluster formation, as the cyclic components in interlocked catenane and rotaxane structures, for constructing assemblies based on macrocycle exo-coordination, for forming columnar stacks, as well as their roles as both structural and redox centres in a range of coordination polymer types are all presented.</P> <P>Graphic Abstract</P><P>This tutorial review highlights the use of macrocyclic ligand complexes as versatile components for the construction of both discrete and polymeric metallo-supramolecular assemblies. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cs35218d'> </P>

Transition and post-transition metal ion chemistry of dibenzo-substituted, mixed-donor macrocycles incorporating five donor atoms

Lindoy, L.F.,Meehan, G.V.,Vasilescu, I.M.,Kim, H.J.,Lee, J.E.,Lee, S.S. Elsevier Publishing Company 2010 Coordination chemistry reviews Vol.254 No.15

The transition and post-transition metal ion chemistry of a wide range of potentially pentadentate dibenzo-substituted macrocyclic ligands incorporating nitrogen, oxygen and/or sulfur donors is reviewed and shown to result in a diverse range of structural types. Aspects of metal ion recognition, bulk membrane transport, systems incorporating appended chromophores, a sulfate binding system, induced Cu(I)/Cu(II) redox switching, coordination polymers, and unsymmetric macrocyclic ligand systems are all discussed.

Recent developments in the thiamacrocyclic chemistry of the latter d-block elements

Kim, S.,Lindoy, L.F.,Lee, S.S. Elsevier Publishing Company 2014 Coordination Chemistry Reviews Vol.280 No.-

In this review we present the metal complexation chemistry of sulfur donor macrocyclic ligands since 2006, including mixed sulfur, nitrogen and/or oxygen systems with the latter d-block metal ions. Both discrete and polymeric systems are discussed.

Assembly of Silver(I)Complexes of Isomeric NS₂-Macrocycles Displaying CyclicOligomer, Helix, and ZigzagStructures

Park, Sunhong,Lindoy, Leonard F.,Lee, Shim Sung American ChemicalSociety 2012 Crystal Growth & Design Vol.12 No.3

<P>An isomeric series of NS<SUB>2</SUB>-macrocycles, incorporating <I>ortho</I>- (<I><B>o</B></I><B>-L</B>), <I>meta</I>- (<I><B>m</B></I><B>-L</B>),and <I>para</I>-xylyl (<I><B>p</B></I><B>-L</B>) groups in their backbones between the sulfur donors, havebeen synthesized. A comparative investigation of the coordinationbehavior of these macrocyclic ligands with silver(I) salts is reported.The X-ray structures of six complexes (<B>1</B>–<B>6</B>) were determined, and a variety of structural types thatrange from cyclic oligomers to zigzag or helical chains is shown tooccur. Reactions of <I><B>o</B></I><B>-L</B> with silver nitrate and perchlorate afforded three complexes withdifferent topologies: the cyclic hexamer [Ag<SUB>6</SUB>(<I><B>o</B></I><B>-L</B>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>6</SUB>·0.5DMF·7H<SUB>2</SUB>O (<B>1</B>), the cyclichexamer with two terminal complex units [Ag<SUB>8</SUB>(<I><B>o</B></I><B>-L</B>)<SUB>8</SUB>](ClO<SUB>4</SUB>)<SUB>8</SUB> (<B>2</B>), and a one-dimensional (1D) zigzag coordinationpolymer of type {[Ag<SUB>2</SUB>(<I><B>o</B></I>-<B>L</B>)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>2</SUB>·2CH<SUB>3</SUB>CN·CHCl<SUB>3</SUB>}<SUB><I>n</I></SUB> (<B>3</B>). Reaction of <I><B>m</B></I>-<B>L</B> with silver(I) perchlorate gave the 1D zigzag coordination polymer,{[Ag(<I><B>m</B></I><B>-L</B>)]ClO<SUB>4</SUB>·CH<SUB>2</SUB>Cl<SUB>2</SUB>}<SUB><I>n</I></SUB> (<B>4</B>). Reaction of <I><B>p</B></I><B>-L</B> with silver perchlorate yielded a crystalline product whose X-rayanalysis confirmed it to be a mixture of two different species: thediscrete helical complex {[Ag<SUB>3</SUB>(<I><B>p</B></I><B>-L</B>)<SUB>3</SUB>](ClO<SUB>4</SUB>)<SUB>3</SUB>}<SUB><I>n</I></SUB> (<B>5</B>) and the cyclic tetramer [Ag<SUB>4</SUB>(<I><B>p</B></I><B>-L</B>)<SUB>4</SUB>(ClO<SUB>4</SUB>)<SUB>4</SUB>]·3DMF (<B>6</B>). The influenceof macrocyclic ring flexibility and sulfur donor atom spacing on thetopologies adopted by the respective complexes is discussed.</P><P>Isomeric NS<SUB>2</SUB>-macrocycles incorporating <I>ortho-</I> (<I><B>o</B></I><B>-L</B>), <I>meta-</I> (<I><B>m</B></I><B>-L</B>),and <I>para-</I>xylyl (<I><B>p</B></I><B>-L</B>) groups in their macrocyclic backbones yielded a rangeof supramolecular Ag(I) complexes with topologies ranging from cyclicoligomers to zigzag and helical chains.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cgdefu/2012/cgdefu.2012.12.issue-3/cg201374g/production/images/medium/cg-2011-01374g_0008.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cg201374g'>ACS Electronic Supporting Info</A></P>

Supramolecular copper(I) halide complexes of O₂S₂X (X = S, O and NH) macrocycles exhibiting dinuclear, 1D- and 2D-coordination polymeric structures

Jo, Minhye,Seo, Joobeom,Lindoy, Leonard F.,Sung Lee, Shim Royal Society of Chemistry 2009 Dalton Transactions Vol.2009 No.31

<P>The effect of varying donor X in otherwise structurally similar O<SUB>2</SUB>S<SUB>2</SUB>X-macrocycles (L<SUP>1</SUP>: X = S, L<SUP>2</SUP>: X = O and L<SUP>3</SUP>: X = NH) on the corresponding assembly reactions with Cu(I) halides has been demonstrated to yield three supramolecular complexes with different architectures: L<SUP>1</SUP> resulted in a discrete dimeric complex (1), while L<SUP>2</SUP> and L<SUP>3</SUP> gave respectively 1D (2) and 2D (3) coordination polymers; the solid state photoluminescence of 3 is also described.</P> <P>Graphic Abstract</P><P>The variation of X in otherwise structurally similar O<SUB>2</SUB>S<SUB>2</SUB>X macrocycles results in three Cu(I) supramolecular complexes all showing unusual structural features. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b906474e'> </P>

Metallacycles derived from metal complexes of exo-coordinated macrocyclic ligands

Lee, E.,Lee, S.Y.,Lindoy, L.F.,Lee, S.S. Elsevier Publishing Company 2013 Coordination chemistry reviews Vol.257 No.21

The assembly of metallacyclic structures incorporating exo-coordinated macrocyclic ligand components is reviewed. The exo-coordination approach provides a means for building extended cyclic assemblies and contrasts with the use of conventional endocyclic macrocyclic coordination which generally results in metal-in-cavity products. The approach, which depends on the availability of one or more donor atoms bearing electron lone pairs that are oriented exo to their macrocyclic cavity, has been employed to produce a range of diverse metallacyclic structures; examples of such metallo-assemblies displaying cyclic dimeric, trimeric, tetrameric, and hexameric topologies are presented.

Assembling latter d-block heterometal coordination polymers: Synthetic strategies and structural outcomes

Lee, E.,Seo, S.,Lee, S.S.,Lindoy, L.F. Elsevier Publishing Company 2017 Coordination Chemistry Reviews Vol.348 No.-

Heterometal coordination polymers are a class of solid-state materials that, compared to related single metal coordination polymers, often display additional steric and electronic complexity, leading to unusual properties and new potential applications. In this report we review synthetic strategies for constructing heterometal polymers along with a discussion of the diverse structural arrays that have been shown to result.

Comparative investigation of the copper(II) complexes of (R)-, (S)- and (R,S)-1-phenyl-N,N-bis(pyridine-3-ylmethyl)ethanamine along with the related complex of (R,S)-1-cyclohexyl-N,N-bis(pyridine-3-ylmethyl)ethanamine. Synthetic, magnetic, and structural

Woo, Arim,Lee, Young Hoon,Hayami, Shinya,Lindoy, Leonard F.,Thué,ry, Pierre,Kim, Yang Springer-Verlag 2011 JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHE Vol.71 No.3

Interaction of silver(I) and copper(I) with an O₂S₂-macrocycle - A comparative structural study

Kim, S.,Lee, E.,Lee, S.Y.,Lee, S.S.,Lindoy, L.F. Elsevier Sequoia [etc.] 2014 Inorganica chimica acta Vol.417 No.-

The 14-membered O<SUB>2</SUB>S<SUB>2</SUB>-macrocycle L reacts with AgPF<SUB>6</SUB> in acetonitrile/dichloromethane (1:1) to yield the cyclic, double S-Ag-S bridged complex, [Ag<SUB>2</SUB>L<SUB>2</SUB>(CH<SUB>3</SUB>CN)<SUB>4</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (2), in which each Ag(I) is bound to two exo-oriented S donors arising from different macrocycles to form a 12-membered, di-Ag metallacycle. Two PF<SUB>6</SUB><SUP>-</SUP> ions form weak intramolecular contacts [Ag...F, 2.925(2)A] between the Ag centres in a bridging bidentate fashion. The coordination sphere of each Ag is completed by two weakly bound acetonitrile molecules. The respective macrocyclic ligands are arranged trans to the mean plane through the metallacycle. When the above synthetic procedure was repeated employing methanol/dichloromethane (1:1) as solvent, a complex of type [Ag<SUB>2</SUB>L<SUB>2</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (3) was obtained whose structure incorporates a similar 12-membered metallacycle but with the respective macrocyclic rings now oriented towards the same side of the metallacyclic plane. The reaction of L with AgCF<SUB>3</SUB>SO<SUB>3</SUB> yields [Ag<SUB>2</SUB>L<SUB>2</SUB>(CF<SUB>3</SUB>SO<SUB>3</SUB>)<SUB>2</SUB>].2CH<SUB>3</SUB>CN (4) whose structure resembles that of [Ag<SUB>2</SUB>L<SUB>2</SUB>(CH<SUB>3</SUB>CN)<SUB>4</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (2); each complex unit incorporates a di-Ag(I) 12-membered metallacycle, with symmetrical bridging bidentate CF<SUB>3</SUB>SO<SUB>3</SUB><SUP>-</SUP> ions weakly linking Ag centres. Long Ag1...Ag1C contacts are present between pairs of complex units. Reaction of Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>PF<SUB>6</SUB> (one equiv.) with L in methanol/dichloromethane (1:1) resulted in isolation of [CuL<SUB>2</SUB>]PF<SUB>6</SUB> (5) incorporating a distorted tetrahedral S<SUB>4</SUB>-coordination sphere, with each macrocycle binding as a bidentate ligand via its two (exo-orientated) S atoms. In contrast, reaction of [Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>]PF<SUB>6</SUB> (two equiv.) with L in either acetonitrile/dichloromethane (1:1) or methanol/dichloromethane (1:1) yielded [Cu<SUB>2</SUB>L<SUB>3</SUB>]PF<SUB>6</SUB> (6) in which the Cu(I) centres are bound exo to the macrocyclic cavity by individual S-donors from one L, with the coordination sphere of each Cu(I) completed by out-of-plane binding of the S<SUB>2</SUB>O donors from a second L. Unsymmetrical F...Cu contacts from a PF<SUB>6</SUB><SUP>-</SUP> anion weakly link the pair of Cu centres in a bridging bidentate fashion.

Interaction of copper(II) with N-substituted bis(2-pyridylmethyl)amine derivatives

Kim, M.,Mora, C.,Lee, Y.H.,Clegg, J.K.,Lindoy, L.F.,Min, K.S.,Thuery, P.,Kim, Y. Elsevier 2010 Inorganic chemistry communications Vol.13 No.10

<P>Interaction of copper(II) with the N-substituted bis(2-pyridylmethyl)amine derivatives, (R)-N-1,N-1-bis (pyridine-2-ylmethyl)butane-1,2-diamine (L-1) and (R)-2-(bis(pyridin-2-ylmethyl)amino)butan-1-ol (L-2), has led to isolation of optically active [Cu(L-1)Cl]PF6 (1) and [Cu(L-2)Cl]ClO4 (2), respectively. The X-ray structures of (1) and (2) show that the copper is bound to all four heteroatoms of the respective ligands as well as to a chlorine atom in a distorted square pyramidal arrangement in which the three nitrogens of L-1 or L-2 occupy three positions of each basal plane while the fourth position is occupied by the chloro ligand; apical sites in each case are filled by the amine donor from the NH2-substituted butane arm in L-1 or the (protonated) alcohol oxygen of the 2-aminobutane-1-ol substituent in L-2. To a first approximation the coordination geometry in 2 is distorted square pyramidal; however, the remaining (axial) site on each copper centre is involved in a long contact (2.96 angstrom) with a bound chloro ligand from an adjacent complex which connects individual complex units in a zigzag 1-D polymeric chain, so that the coordination geometry could also be seen as pseudo-octahedral. A temperature-dependent magnetic study revealed the presence of ferromagnetic exchange coupling between copper centres in the chain reflecting the orthogonal structure between the chloro-bridged copper(II) ions; in contrast, and as expected, the discrete complex 1 is magnetically dilute. (C) 2010 Elsevier B.V. All rights reserved.</P>