Mixed Donor Macrocyclic Ligands Research Articles

Silver(I) coordination polymers based on nitrile-functionalized mixed-donor ligands of different flexibility

The nitrile-functionalized derivatives of 2,8-dithia-5-aza-2,6-pyridinophane ([12]anePyNS2)(Py = Pyridine), 1-aza-4,7,10-trithiacyclododecane ([12]aneNS3), and N,N’-bis(2-pyridylmethyl)-propylenediamine (Pypn), referred to as L10, L11 and L12, respectively, have been prepared. Following the reaction of these ligands with silver(I) salts, the three coordination polymers (CPs) {[Ag(L10)](BF4)}∞, {[Ag(L11)](BF4)∙½MeCN}∞, and {[Ag(L12)](NO3)}∞, have been isolated and structurally characterized. The structural features of the three CPs depends more on the nature of the un-functionalized ligands rather than on the presence of the nitrile groups. A comparative analysis of the structures of the three CPs is performed in relation to the structures of polymeric silver(I) compounds obtained with nitrile-functionalized pendant arms of related aza- and mixed donor macrocyclic ligands (L1–L9) reported in the literature.

Can Serendipity Still Hold Any Surprises in the Coordination Chemistry of Mixed-Donor Macrocyclic Ligands? The Case Study of Pyridine-Containing 12-Membered Macrocycles and Platinum Group Metal Ions PdII, PtII, and RhIII.

This study investigates the coordination chemistry of the tetradentate pyridine-containing 12-membered macrocycles L1-L3 towards Platinum Group metal ions PdII, PtII, and RhIII. The reactions between the chloride salts of these metal ions and the three ligands in MeCN/H2O or MeOH/H2O (1:1 v/v) are shown, and the isolated solid compounds are characterized, where possible, by mass spectroscopy and 1H- and 13C-NMR spectroscopic measurements. Structural characterization of the 1:1 metal-to-ligand complexes [Pd(L1)Cl]2[Pd2Cl6], [Pt(L1)Cl](BF4), [Rh(L1)Cl2](PF6), and [Rh(L3)Cl2](BF4)·MeCN shows the coordinated macrocyclic ligands adopting a folded conformation, and occupying four coordination sites of a distorted square-based pyramidal and octahedral coordination environment for the PdII/PtII, and RhIII complexes, respectively. The remaining coordination site(s) are occupied by chlorido ligands. The reaction of L3 with PtCl2 in MeCN/H2O gave by serendipity the complex [Pt(L3)(μ-1,3-MeCONH)PtCl(MeCN)](BF4)2·H2O, in which two metal centers are bridged by an amidate ligand at a Pt1-Pt2 distance of 2.5798(3) Å and feature one square-planar and one octahedral coordination environment. Density Functional Theory (DFT) calculations, which utilize the broken symmetry approach (DFT-BS), indicate a singlet d8-d8 PtII-PtII ground-state nature for this compound, rather than the alleged d9-d7 PtI-PtIII mixed-valence character reported for related dinuclear Pt-complexes.

Influence of the Number of Metallophilic Interactions and Structures on the Optical Properties of Heterometallic Au/Ag Complexes with Mixed-Donor Macrocyclic Ligands.

The reactivity of the polymeric gold(I)/silver(I) compound [Au2Ag2(C6F5)4(OEt2)2] n toward the 12-membered mixed-donor macrocyclic ligands 1,7-diaza-4,10-dithiacyclododecane (L1), 1-aza-4,7,10-trithiacyclododecane (L2), N-quinolinylmethyl-1-aza-4,7,10-trithiacyclododecane (L3), and N, N'-bis(quinolinylmethyl)-1,7-diaza-4,10-dithiacyclododecane (L4) was studied. The reactions were carried out using different molar ratios depending on the coordination properties of the ligands, which were modified by changing the donor atoms present in the macrocyclic framework (sulfur or nitrogen) or by linking one or two methylquinoline pendant-arms at the secondary nitrogen atom(s). X-ray diffraction analysis of the new complexes obtained show a nuclearity that increases on increasing the number of donor atoms in the ligands. The rich structural diversity observed determines different optical responses when the complexes are irradiated with UV-vis light in the solid state and in THF solution. The study of the optical properties reveals that in complexes for which the luminescence is due to metal-metal interactions, higher emission wavelengths are observed as the number of these metallophilic contacts increases, while the luminescence of ionic complexes has its origin in the macrocyclic ligands. TD-DFT calculations were carried out to verify the origin of these interesting structural-optical property relationships.

Synthesis of metal-free and zinc phthalocyanines containing 2-pyridyl-methyl pendant arm linked with NS4-donor macrocyclic moiety and their selectivity towards Cu(II) cations

New phthalonitrile (L1), metal-free phthalocyanine (H2Pc) and zinc-phthalocyanine (ZnPc) substituted in peripheral positions with 2-pyridyl methyl pendant arm linked mixed donor macrocyclic ligands have been prepared in a multi-step reaction sequence. The novel compounds were characterized by a combination of elemental anlaysis, 1 H NMR, 13 C NMR, IR, UV-vis and MS spectral data. The influence of metal cations such as Cd 2+, Zn 2+, Hg 2+, Al 3+, Fe 3+ and Cu 2+ on the spectroscopic properties of dinitrile compound L1 and free phthalocyanine H2Pc was investigated by means of absorption spectrophotometry. Spectrophotometric titrations were carried out with these ligands for Cu 2+ ion. The complex composition of Cu - L1 was found 1:1 by means of spectrophotometric titration data. The spectrophotometric method showed good sensitivity for Cu 2+ with linear range of 2.6 × 10-6 to 1.3 × 10-4 M with dinitrile compound.

Interaction of Mixed-Donor Macrocycles Containing the 1,10-Phenanthroline Subunit with Selected Transition and Post-Transition Metal Ions: Metal Ion Recognition in Competitive Liquid−Liquid Solvent Extraction of CuII, ZnII, PbII, CdII, AgI, and HgII

Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L(4)) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L(7)) have been synthesized and characterized. The coordination behavior of L(4) and L(7) toward the metal ions Cu(II), Zn(II), Pb(II), Cd(II), Hg(II), and Ag(I) was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by (1)H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L(1)-L(3), L(5), L(6): all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L(4) and L(7). The complexes [Cd(NO3)2(L(5))], [Pb(L(7))](ClO4)2 x 1/2MeCN, [Pb(L(4))](ClO4)2 x MeCN, and [Cu(L(7))](ClO4)2 x 3/2MeNO2 were characterized by X-ray crystallography. The efficacy of L(1)-L(7) in competitive liquid-liquid metal ion extraction of Cu(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II) was assessed. In the absence of Hg(II), a clear extraction selectivity for Ag(I) was observed in all systems investigated.

Coordination chemistry of N-aminopropyl pendant arm derivatives of mixed N/S-, and N/S/O-donor macrocycles, and construction of selective fluorimetric chemosensors for heavy metal ions

The coordination chemistry of the N-aminopropyl pendant arm derivatives (L1c-4c) of the mixed donor macrocyclic ligands [12]aneNS2O, [12]aneNS3, [12]aneN2SO, and [15]aneNS2O2(L1a-4a) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) in aqueous solution has been investigated. The protonation and stability constants with the aforementioned metal ions were determined potentiometrically and compared, where possible, with those of the unfunctionalised macrocycles. The measured values show that Hg(II) and Cu(II) in water have the highest affinity for all ligands considered, with the N-aminopropyl pendant arm weakly coordinating the metal centres. Crystals suitable for X-ray diffraction analysis were grown for the perchlorate salt (H2L1c)(ClO4)2.dmf, and for the 1 : 1 complexes [Cd(L3a)(NO3)2](1), [Cu(L4a)dmf](ClO4)2(2), [Zn(L1c)(ClO4)]ClO4(3), [Cd(L1c)(NO3)]NO3(4), and [Hg(L2c)](ClO4)2(5). Their structures show the macrocyclic ligands adopting a folded conformation, which for the 12-membered systems can be either [2424] or [3333] depending on the nature of the metal ion. L1c-4c were also functionalised at the primary amino pendant group with different fluorogenic subunits. In particular the N-dansylamidopropyl (Lnd, n= 1-4), and the N-(9-anthracenylmethyl)aminopropyl (Lne, n= 1, 2, 4, ) pendant arm derivatives of L1a-4a were synthesised and their optical responses to the above mentioned metal ions were investigated in MeCN/H2O (4 : 1 v/v) solutions.

Nitrile functionalised pendant-arm derivatives of aza- and mixed donor macrocyclic ligands as new building blocks for inorganic crystal engineering

Download options Please wait... Supplementary files Crystal structure data TXT (120K) Article information DOI https://doi.org/10.1039/B110134J Article type Paper Submitted 16 Nov 2001 Accepted 24 Jan 2002 First published 26 Mar 2002 Download Citation J. Chem. Soc., Dalton Trans., 2002, 1662-1670 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Nitrile functionalised pendant-arm derivatives of aza- and mixed donor macrocyclic ligands as new building blocks for inorganic crystal engineering L. Tei, A. J. Blake, P. A. Cooke, C. Caltagirone, F. Demartin, V. Lippolis, F. Morale, C. Wilson and M. Schröder, J. Chem. Soc., Dalton Trans., 2002, 1662 DOI: 10.1039/B110134J To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Lorenzo Tei Alexander J. Blake Paul A. Cooke Claudia Caltagirone Francesco Demartin Vito Lippolis Francesca Morale Claire Wilson Martin Schröder

New Macrocyclic Ligands. XIV. Synthesis and X-Ray Structures of Potentially Pentadentate Ligands Incorporating Non-Symmetrically Arranged N4S-, N3OS-, N2O2S- and N2S2O-Heteroatoms

The synthesis and characterization of new mixed-donor macrocyclic ligands incorporating nitrogen, sulfur and/or oxygen heteroatoms are described. The new 17- or 18-membered macrocyclic rings contain unsymmetrical arrangements of their heteroatoms in contrast to related, previously reported rings in which the donor sets are arranged symmetrically. The X-ray structures of the 17-membered rings incorporating N4O- and N4S-donor sets are presented.

Macrocyclic Complexes of Niobium(III): Synthesis, Structure, and Magnetic Behavior of Mononuclear and Dinuclear Species That Incorporate the [P2N2] System

The coordination chemistry of the two mixed donor macrocyclic ligands R[P2N2] (where R[P2N2] = RP(CH2SiMe2NSiMe2CH2)2PR, R = cyclohexyl (Cy) or phenyl (Ph)) with niobium(III) is presented. The reaction of the dilithio precursors R[P2N2]Li2(S) (R = Cy, S = THF; R = Ph, S = 1,4-dioxane) with NbCl3(DME) (DME = 1,2-dimethoxyethane) generates the complexes R[P2N2]NbCl (R = Cy, 1; R = Ph, 2). For R = Cy, single-crystal X-ray diffraction studies and variable-temperature magnetic susceptibility measurements indicate that 1 is mononuclear in the solid state; however, analogous variable-temperature magnetic data suggest that 2 is dinuclear in the solid state due to the observation of antiferromagnetic exchange. In solution, 2 is apparently monomeric similar to 1. Adduct formation between these mononuclear complexes is also evident; reaction of 2 with neutral donors and coordinating solvents produces the mononuclear derivatives Ph[P2N2]NbCl(L) (L = py, CO, PMe3, THF, MeCN), of which the pyridine adduct, 3e, has been...

Macrocyclic ligand design: Structure—function relationships involving the interaction of cobalt(II), nickel(II) and copper(II) with mixed donor macrocyclic ligands

A comparative investigation of the interaction of Co(II), Ni(II) and Cu(II) with a series of mixed-donor dibenzo-substituted macrocyclic ligands, incorporating O 2N 3-, O 2N 4-, O 3N 2-, O 3N 3- and O 4N 2-donor sets, has been carried out. The thermodynamic stabilities of the respective complexes in 95% methanol ( I = 0.1; Et 4NClO 4, 25°C) have been determined. All ligands form 1:1 (metal:ligand) species with the above metal ions although, in a few instances, species of type MLH 2+ were also detected. In an attempt to elucidate ligand structure/function relationships, an analysis of the effect of variation of ligand backbone and/or donor atom set on the respective complex stabilities has been carried out; the results are compared with those obtained previously for related mixed-donor (cyclic) systems. The X-ray structure of the nickel(II) nitrate complex of the O 3N 3-donor macrocycle (V) is presented. C 23H 35N 5NiO 10 crystallised in the monoclinic space group P2 1/ n, with a = 17.201(3), b = 11.341(2), c = 14.742(3) Å, β = 104.34(2)° and Z = 4.

Macrocyclic Ligand Design. Structure - Function Relationships Underlying the Interaction of Zinc(II), Cadmium(II), Silver(I) and Lead(II) with Mixed-Donor Macrocyclic Ligands

An investigation of the interaction of zinc(II), cadmium(II), silver(I) and lead(II) with a series of mixed-donor dibenzo-substituted macrocyclic ligands, incorporating O2N3-, O2N4-, O3N2-, O3N3-, O4N2- and O2N3S-donor sets, has been carried out. The log K values for the respective complexes in 95% methanol (I = 0·1; Et4NClO4, 25°C) have been determined potentiometrically. All ligands form 1 : 1 (metal/ligand) complexes with the above metal ions although in isolated cases species of type MLH2+ were also observed. An investigation of the effect of variation of ligand structure on the respective complex stabilities has been carried out and the results compared with those obtained previously for closely related mixed-donor macrocyclic systems. The binding of silver(I) and lead(II) to the 17- and 18-membered O3N2-ligand systems has been assessed in (CD3)2SO by means of 13C n.m.r. spin–lattice relaxation (T1) studies as well as by observation of the induced chemical shifts of particular ligand resonances on complex formation. Overall, the n.m.r. results correlate well with the observed thermodynamic stabilities of the individual complexes.

Dalton communications. Metal-ion recognition. Donor-set control of silver(I)/lead(II) discrimination using mixed-donor macrocyclic ligands

Download options Please wait... Article information DOI https://doi.org/10.1039/DT9940000237 Article type Paper Download Citation J. Chem. Soc., Dalton Trans., 1994, 237-238 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Dalton communications. Metal-ion recognition. Donor-set control of silver(I)/lead(II) discrimination using mixed-donor macrocyclic ligands K. R. Adam, D. S. Baldwin, A. Bashall, L. F. Lindoy, M. McPartlin and H. R. Powell, J. Chem. Soc., Dalton Trans., 1994, 237 DOI: 10.1039/DT9940000237 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Kenneth R. Adam Darren S. Baldwin Alan Bashall Leonard F. Lindoy Mary McPartlin Harold R. Powell

New bis(ferrocenecarbonyl)- and bis(ferrocenyl)-appended diazatetrathia mixed-donor macrocyclic ligands and their copper-(II) and -(I) complexes

New bis(ferrocenecarbonyl)-, bis(ferrocenyl)- and dibenzyl-appended diazatetrathia mixed-donor macrocyclic ligands L1, L2 and L3 have been prepared. Copper-(II) and -(I) complexes of these ligands have been isolated and characterised. Single-crystal X-ray structures of 7,16-bis(ferrocenemethyl)-1,4,10,13-tetrathia-7,16-diazacyclooctadecane (L2) and of its copper(I) complex [CuL2]PF6 have also been determined. Electrochemical investigations reveal the respective ferrocene–ferrocenium redox couples of ligands L1 and L2 are perturbed to more positive potentials on co-ordination of the copper(II) ion. These copper(II) complexes also exhibit quasi-reversible copper(II)–copper(I) redox couples at negative potentials (versus saturated calomel electrode).

ChemInform Abstract: Mixed Donor Macrocyclic Ligands. Comparative X‐Ray Diffraction, IR, and Fast Atom Bombardment Mass Spectrometric Studies of the Nickel Thiocyanate Complexes of Three O2N3‐Donor Macrocycles.

AbstractMinor changes in the substitution pattern of the backbone of the 17‐membered macrocyclic ring (I) incorporating O2N3 donor atoms have been demonstrated to have a significant influence on the ligand coordination modes in the corresponding Ni thiocyanate complexes of the type NiL(NCS)2·nH2O (L: (I); n: 0, 0.5, or 1).

Comparative Calorimetric and 1H N.M.R. Studies of the Interaction of Ag(I) With a Series of Mixed-Donor Macrocycles Incorporating Nitrogen, Oxygen and or Sulfur Donor Atoms

The interaction of silver ion with a range of mixed-donor macrocyclic ligands incorporating nitrogen, oxygen and/or sulfur donors has been investigated. Complementary calorimetric and n.m.r. studies in acetonitrile (and its deuterated derivative) were used to investigate the nature of the equilibria present as the metal/ ligand ratio was varied. In all systems the formation of a 1 : 1 species was observed, with a 1:2 (metal/ ligand ) species also being formed in the presence of excess ligand in the majority of cases. Enthalpies of formation for the various complexes have been determined. Stepwise stability constants for the respective [ AgL ]+ + L ↔ [AgL2]+ equilibria have been estimated from the calorimetric titration data, and the factors promoting the formation of the 1:2 species are discussed. The studies confirm the enhanced affinity of AgI for thioether donors over ether donors.

Studies involving mixed-donor macrocyclic ligands. A comparative study of the influence of medium effects on the stabilities of complexes of Co II , Ni II , and Cu II with 14- to 16-membered O2N2-donor macrocycles

The effect of change of background electrolyte and solvent from 95% methanol (I= 0.1 mol dm–3, NEt4ClO4 or NMe4Cl) to 65% ethanol (I= 0.1 mol dm–3, NMe4NO3) on the stability constants of a series of complexes of CoII, NiII, and CuII with 14- to 16-membered O2N2-macrocycles has been investigated. The present study does not substantiate the results of a previous study, in which the latter conditions were employed, when it was proposed that a different stability order occurs for the complexes of the 14- and 16-membered macrocycles than reported for these complexes in 95% methanol (I= 0.1 mol dm–3, NMe4Cl). Instead, it was found that the same stability order is maintained no matter which of the above conditions is employed for the measurements. In the case of the nickel(II) complexes, the stability increases from the 14- to the 16-membered ring in accordance with the previous prediction that the fit of the latter ring is nearly ideal for high-spin NiII.

ChemInform Abstract: Heavy Metal Chemistry of Mixed Donor Macrocyclic Ligands. Strategies for Obtaining Metal Ion Recognition

ChemInformVolume 18, Issue 33 Reviews ChemInform Abstract: Heavy Metal Chemistry of Mixed Donor Macrocyclic Ligands. Strategies for Obtaining Metal Ion Recognition L. F. LINDOY, L. F. LINDOY Dep. Chem. Biochem., James Cook Univ., Townsville, Aust.Search for more papers by this author L. F. LINDOY, L. F. LINDOY Dep. Chem. Biochem., James Cook Univ., Townsville, Aust.Search for more papers by this author First published: August 18, 1987 https://doi.org/10.1002/chin.198733394Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume18, Issue33August 18, 1987 RelatedInformation

Studies involving mixed donor macrocyclic ligands. Comparative X-ray diffraction, infrared, and fast atom bombardment mass spectrometric studies of the nickel thiocyanate complexes of three O2N3-donor macrocycles

Minor changes in the substitution pattern of the backbone of a 17-membered macrocyclic ring incorporating O2N3 donor atoms have been demonstrated to have a significant influence on the ligand co-ordination modes in the corresponding nickel thiocyanate complexes. Comparative i.r. and fast atom bombardment (f.a.b.) source mass spectrometry as well as X-ray diffraction studies (on three complexes) have been used to elucidate the nature of the species formed. A variety of structures occurs for these complexes: three of the complexes are monomeric and incorporate terminal isothiocyanato groups with the 1,4,7-triazaheptane macrocyclic fragment co-ordinating in either a facial or meridional manner. Two forms of the complex of the unsubstituted macrocycle were isolated. The more insoluble form is dimeric and incorporates unusual N-bridged isothiocyanato groups. The combination of i.r. and f.a.b. mass spectrometric studies has proven to be especially useful for structural elucidation in systems of the type investigated.