Synthesis and characterization of three Cd(II) Schiff-base macrocyclic N3O2 complexes

Three polyamine ligands of N1-(2-nitrobenzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L₁), N1-(2-nitrobenzyl)-N1-(2-aminoethyl)propane-1,3-diamine (L₂) and N1-(2-nitrobenzyl)-N1-(3-aminopropyl)propane-1,3-diamine (L₃) were synthesized and their cyclocondensation with 2-[2-(2-formyl phenoxy)ethoxy]benzaldehyde (L₄) in the presence of various metal(II) ions was examined. These reactions only in the presence of a stoichiometric amount of cadmium(II) nitrate gave the related cadmium(II) macrocyclic Schiff-base complexes. In all the other cases no cyclic complexes have been obtained and metal(II) polyamines were the only products. The complexes have been studied with IR, ¹H NMR, ¹³C NMR, DEPT, COSY, HMQC and microanalysis. The crystal structures of [Cd(NO₃)(L₅)(μ-NO₃)Cd(NO₃)(L₅)]0.5Cd(NO₃)₄ (1) and [CdL₅(NO₃)(CH₃OH)]ClO₄ (2) have been also determined.     

Synthesis of two new tripodal ligands and their cyclocondensation with 2-[2-(2-formylphenoxy)ethoxy]benzaldehyde in the presence of manganese(II) and cadmium(II) metal ions

Two new asymmetric tripodal tetraamine ligands, 2-((bis(2-aminoethyl)amino)methyl)benzenamine (L²) and 2-(((2-aminoethyl)(3-aminopropyl)amino)methyl)benzenamine (L³) were synthesized and characterized. [1+1] Macrocyclic Schiff-base complexes containing 1,2-diphenoxyethane head units and a 2-aminobenzyl pendant arm, were synthesized as [MnL⁴(MeOH)](ClO₄)₂ (1), [MnL⁵(MeOH)](ClO₄)₂ (2), [CdL⁴(H₂O)](NO₃)₂ (3) and [CdL⁵(H₂O)](NO₃)₂ (4) from the metal ion templated cyclocondensation reactions of 2-[2-(2-formylphenoxy)ethoxy]benzaldehyde with the (L²) or (L³) tripodal tetraamine ligands. The crystal structure determination of (1) and (4) showed that the complex cations that had formed consisted of pentagonal bipyramidally coordinated Mn(II) and Cd(II) ions, centrally located in a N₃O₂ macrocycle, with one 2-aminobenzyl pendant arm. Supporting ab initio HF-MO calculations have been undertaken using the standard 3-21G^∗ and 6-31G^∗ basis sets.     

Synthesis and crystal structures of Cd(II) complexes with di-pyridyl hexa-azamacrocyclic ligands having cyano pendant-arms

The coordination capability of two pendant-armed azamacrocyclic ligands with cyanoethyl L¹and cyanomethyl L² pendant groups towards cadmium nitrate and perchlorate salts was achieved. All metal complexes were characterized by elemental analysis, LSI-MS, IR, conductivity measurements and ¹H NMR spectroscopy. The X-ray crystal structure of the complexes [CdL¹](NO₃)₂, [CdL¹](ClO₄)₂ · CH₃CN, and [CdL²](ClO₄)₂ · H₂O were also determined. All the complexes are mononuclear with the metal ion in a distorted octahedral environment. The pendant groups are not coordinated to the metal due the linear nature of the cyano groups; however, different interactions between nitrate ions, nitrile groups and pyridine rings from the macrocycle have been observed in the Cd(II) complexes with L¹.     

Synthesis and Characterization of Metal Complexes of two Novel Pyridine‐Derived Macrocyclic Ligands Bearing o‐ and p‐Nitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the two secondary aminic groups of the oxaazamacrocyclic precursor L with o‐nitrobenzylbromide (L¹) or p‐nitrobenzylbromide (L²). Metal complexes of L¹ and L² have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, ¹H and ¹³C NMR spectroscopy and magnetic studies. Crystal structures of ligands L¹ and L², as well as complexes [CdL¹(NO₃)₂]·2CH₃CN and [Ag₂Br(L²)₂](ClO₄)·2CH₃CN have been determined by single crystal X‐ray crystallography.     

Synthesis and characterization of some new Co(II) and Cd(II) macroacyclic Schiff-base complexes containing piperazine moiety

Three Cd(II) or Co(II) macroacyclic Schiff-base complexes [CoL¹Br]ClO₄ (1), [CdL²Cl]ClO₄ (2) and [CdL³(NO₃)]ClO₄ (3) were prepared by template condensation of 2-pyridinecarboxaldehyde and three different amines containing piperazine moiety, N,N′-bis(2-aminoethyl)piperazine, N,N′(2-aminoethyl)(3-aminopropyl)piperazine and N,N′-bis(3-aminopropyl)piperazine, in the presence of Co(II) or Cd(II) metal ions, respectively. All complexes have been studied with IR, FAB mass and microanalysis and for complex (3) by ¹H and ¹³C NMR spectra. One of these complexes, [CdL³(NO₃)]ClO₄ (3) has been characterized through X-ray crystallography. In complex (3), the Cd(II) ion is coordinated by the six nitrogen donor atoms from the ligand and by one oxygen atom from a monodentate nitrate ion in a N₆O environment.     

Synthesis and characterization of some new Cd(II) and Zn(II) macrocyclic Schiff base complexes derived from cyclocondensation of three new linear aromatic (N4) amines and 2,6-diacetylpyridine. Crystal structure and biological activity studies

Six new Cd(II) and Zn(II) macrocyclic Schiff base complexes from cyclocondensation of 2,6-diacetylpyridine and three different liner aromatic amines have been investigated. The resulting ligands, L¹ and L² are 17- and L³ 18-membered pentaaza macrocycles. The complexes have been characterized by a variety of methods such as IR, elemental analysis, EI-Mass and conductivity measurements and in the case of cadmium complex by ¹H and ¹³C NMR spectroscopy. The crystal structure of [CdL¹(CH₃OH)](ClO₄)₂ has been determined. In this complex, the Cd(II) ion is coordinated to five nitrogen donor atoms of the ligand and one oxygen atom from methanol in a N₅O environment. The geometry around the cadmium can be better described as in a slightly distorted pentagonal-pyramidal. The synthesized compounds have antibacterial activity against the three gram-positive bacteria: S. aureus, B. cereus and C. xerosis, and also against the three gram-negative bacteria: E. coli, K. pneumoniae and P. vulgaris. The results show that the antibacterial activity of cadmium complexes is greater than that of zinc complexes.     

Cd(ΙΙ) and Mn(ΙΙ) complexes of a new hexadentate Schiff base ligand derived from an asymmetric tripodal tetraamine and 2-pyridinecarboxaldehyde

Two new compounds, [CdL_22pyfp(NO₃)](ClO₄) (1) and [MnL_22pyfpCl](ClO₄) (2), were prepared by the template condensation of a previously known ligand, (L_22py), and 2-pyridinecarboxaldehyde in the presence of Cd(NO₃)₂ · 4H₂O or MnCl₂ · 4H₂O in equimolar ratios. The resulting compounds were characterized by elemental analysis, IR and single crystal X-ray diffraction, and by NMR in the case of the Cd(II) complex. The Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron. The environment around the Mn(II) ion may be described as a distorted pentagonal bipyramid. The ¹H NMR spectrum of the cadmium complex shows the signal of the imine proton to have two satellites (³J = 44.4 Hz) with intensities of 1:6:1 due to coupling with the neighboring ^111/113Cd atom. The electronic spectra of both complexes, as well as the ligand, is explained on the basis of TD-DFT calculations.     

Synthesis, crystal structure and spectroscopic properties of some cadmium(II) complexes with three polyamine and corresponding macroacyclic Schiff base ligands

Three Cd(II) macroacyclic Schiff base complexes [CdL⁴(NO₃)₂] (4), [CdL⁵(NO₃)₂] (5), [CdL⁶(NO₃)₂] (6) were prepared by template condensation of 2-pyridinecarboxaldehyde with N1-(2-nitrobenzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L¹), N1-(2-nitrobenzyl)-N1-(2-aminoethyl)propane-1,3-diamine (L²) or N1-(2-nitrobenzyl)-N1-(3-aminopropyl)propane-1,3-diamine (L³), in the presence of cadmium metal ion, respectively. Three Cd(II) complexes with L¹, L² and L³ were also synthesized. All complexes have been studied with IR, ¹H NMR, ¹³C NMR, DEPT, COSY, HMQC and microanalysis. Two of these complexes, [CdL⁴(NO₃)₂] (4) and [CdL¹(NO₃)₂] (1) have been characterized through X-ray crystallography. In complex 4, the Cd is in a six-coordinate environment comprised of the ligand N₄-donor set and two oxygen atoms of two nitrate groups. In the polyamine complexes (1, 2 and 3) Cd and ligand are in a ratio of 1:1. Supporting ab initio HF-MO calculations have been undertaken using the standard 3-21G^∗ and 6-31G^∗ basis sets.     

Synthesis, X-ray characterization, NMR and ab initio molecular-orbital studies of some cadmium(II) macrocyclic Schiff-base complexes with two 2-aminoethyl pendant arms

Three new pendant arm Schiff-base macrocyclic complexes, [CdLⁿ]²⁺ (n = 5, 6, 7), have been prepared via cyclocondensation of 2,6-diacetylpyridine with three different branched hexaamines in the presence of Cd(II). The ligands are 15-, 16- and 17-membered pentaaza macrocycles having two 2-aminoethyl pendant arms [L⁵ = 2,13-dimethyl-6,9-bis(aminoethyl)-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L⁶ = 2,14-dimethyl-6,10-bis(aminoethyl)-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene and L⁷ = 2,15-dimethyl-6,11-bis(aminoethyl)-3,6,11,14,20-pentaazabicyclo[14.3.1]eicosa-1(20),2,14,16,18-pentaene]. All complexes were investigated by IR, ¹H and ¹³C NMR, COSY(H,H) and HETCOR(H,C) spectroscopy and X-ray diffraction. In the solid state structure of each complex the Cd(II) ion is situated centrally within an approximately planar pentaaza macrocyclic ring, binding to the five nitrogen atoms, and also to the two pendant amines which are located on opposite sides of the macrocyclic plane. ab initio HF-MO calculations using a standard 3-21G* basis set have been used to verify that these similar basic structures correspond to energy minima in the gas phase.     

Complexation of 4-amino-1,3 dimethyl-2,6 pyrimidine-dione derivatives with cobalt(II) and nickel(II) ions: synthesis,spectral, thermal and antimicrobial studies

Four heterocyclic Schiff-base ligands derived from condensation of 4-amino-1,3 dimethyl-2,6 pyrimidine-dione with 2-hydroxybenzaldehyde, 2-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde and 4-(dimethylamino) benzaldehyde, (HL¹, L², HL³and L⁴), respectively, and their Co(II) and Ni(II) complexes have been prepared and characterized via elemental analysis, molar conductance, magnetic moment, thermal and XRPD analysis as well as spectral data (IR, ¹H-NMR, mass and solid reflectance). IR data reveal that the ligands are bidentate neutral ligands except HL¹, which is monobasic tridentate with coordination sites azomethine (N), carbonyl (O) and phenolic (O). Conductance data suggest that all complexes are non-electrolytes, except cobalt(II) complexes of L²and HL³are 1 : 1 electrolytes. The mass spectra confirm the proposed structure of the ligands and their complexes. The solid reflectance spectral data and magnetic moment measurements suggest octahedral, tetrahedral and square planar geometrical structures for the metal complexes. The spectral data were utilized to compute the important ligand field parameters B, β and Dq; LFSE also was calculated. The thermal behavior is also studied. Antibacterial and antifungal properties of the ligands and their complexes show broad-spectrum activities and the metal complexes show higher activity than the free ligands.     

Synthesis and physiochemical studies on binuclear Cu(II) complexes derived from 2,6-[(N-phenylpiperazin-1-yl)methyl]-4-substituted phenols

Preparation of the ligands HL¹ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-ethylphenol; HL² = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-methoxyphenol and HL³ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-nitrophenol are described together with their Cu(II) complexes with different bridging units. The exogenous bridges incorporated into the complexes are: hydroxo [Cu₂L(OH)(H₂O)₂](ClO₄)₂.H₂O (L¹=1a, L² =1b, L³ =1c), acetato [Cu₂L(OAc)₂]ClO₄.H₂O (L¹ =2a, L² =2b, L³ =2c) and nitrito [Cu₂L¹(NO₂)₂(H₂O)₂]ClO₄.H₂O (L¹=3a, L² =3b, L³ =3c). Complexes1a,1b,1c and2a,2b,2c contain bridging exogenous groups, while3a,3b,3c possess only open μ-phenolate structures. Both the ligands and complexes were characterized by spectral studies. Cyclic voltammetric investigation of these complexes revealed that the reaction process involves two successive quasireversible one-electron steps at different potentials. The first reduction potential is sensitive to electronic effects of the substituents at the aromatic ring of the ligand system, shifting to positive potentials when the substituents are replaced by more electrophilic groups. EPR studies indicate very weak interaction between the two copper atoms. Various covalency parameters have been calculated.     

Synthesis and complexation of two new phenylaminoglyoxime ligands

Two new soluble phenylaminoglyoxime ligands, 4-isopropylanilinephenylglyoxime (L¹H₂), 4-benzylpiperidinephenylglyoxime (L²H₂), were prepared by reacting 4-isopropylaniline and 4-benzylpiperidine with chlorophenylglyoxime. Mononuclear nickel(II), cobalt(II), copper(II), zinc(II), and cadmium(II) complexes with these ligands were synthesized. On the basis of the magnetic and spectral evidence a square-planar geometry for Ni(II) and Cu(II) complexes, a tedrahedral geometry for Cd(II) and Zn(II) complexes and octahedral geometry for Co(II) complexes are proposed. These compounds were elucidated by elemental analysis, IR, UV-Vis, and magnetic moments. The ligands were additionally characterized by ¹H NMR and ¹³C NMR spectra.     

Synthesis and spectroscopic characterization of a new macrocyclic Schiff base formed by the reaction of 1,5- bis (2-formylphenyl)pentane and 2,6-diaminopyridine,and a study of its metal complexes

A new dialdehyde 1,5-bis(2-formylphenyl)pentane was synthesized from 1,5-dibromopentane with salicylaldehyde and K₂CO₃; macrocyclic ligand was synthesized by reaction of 2,6-diaminopyridine and 1,5-bis(2-formylphenyl)pentane. Cu(II), Ni(II), Pb(II), Zn(II), Cd(II) and La(III) complexes were synthesized by reaction of the ligand and Cu(ClO₄)₂ · 6H₂O, Ni(ClO₄)₂ · 6H₂O, Pb(ClO₄)₂ · 6H₂O, Zn(ClO₄)₂ · 6H₂O, Cd(ClO₄)₂ · 6H₂O and La(ClO₄)₃ · 6H₂O, respectively. The ligand and its metal complexes have been characterized by elemental analysis, IR, ¹H and ¹³C NMR, UV–Vis spectra, magnetic susceptibility, conductivity measurements and mass spectra. All complexes are diamagnetic and Cu(II) complex is binuclear.     

Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N,N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

Metal Complexes with N₂O₂S₂ Donor Set. Synthesis and Characterization of the Cobalt(II), Nickel(II), and Copper(II) Complexes of a 15‐ and a 16‐Membered Bis(2‐hydroxyethyl) Pendant Macrocyclic Ligand The macrocyclic ligands 6, 10‐bis(2‐hydroxyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecine ( 1 ) (L¹) and 5, 13‐bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecine (L⁴) have been prepared. They form the stable complexes [CoL¹(‐H)CoL¹](ClO₄)₃ ( 2 ), [NiL¹](ClO₄)₂·MeOH ( 3 ), Λ‐[CuL¹](ClO₄)₂·MeOH ( 4a ) and rac‐[CuL¹](ClO₄)₂·MeOH ( 4b ), [NiL⁴](ClO₄)₂ ( 5 ), and [CuL⁴](ClO₄)₂ ( 6 ). The compounds 1 to 6 have been characterized by standard methods and single‐crystal X‐ray diffraction. In the complexes 2 to 6 the metal atoms are octahedrally coordinated by the N₂O₂S₂ donor set of the ligands. L¹ and L⁴ are folded herein along the N···M···S‐ and the N···M···N′‐axes, respectively. This results at the metal atom in a all‐cis‐configuration for the complexes of L¹ and a trans‐N₂‐cis‐O₂‐cis‐S₂‐configuration for the complexes of L⁴. The cobalt(II) complex 2 is a dimer, bridged by a rather short hydrogen bridge of 2.402(12)Å length. The copper(II) complexes of L¹ and L⁴ differ with respect to the Jahn‐Teller‐distortion.     

Synthesis,Structural, and Antibacterial Studies of Some Mixed Ligand Complexes of Zn(II), Cd(II), and Hg(II) Derived From Citral Thiosemicarbazone and N-Phthaloyl Amino Acids

A series of new mixed ligand complexes of Zn(II), Cd(II), and Hg(II) with cis-3,7-dimethyl-2,6-octadienthiosemicarbazone (CDOTSC; LH) and N-phthaloyl amino acids (AH) have been synthesized by the reaction of metal dichloride with ligands CDOTSC and N-phthaloyl derivative of DL-glycine (A₁H), L-alanine (A₂H), or L-valine (A₃H) in a 1:1:1 molar ratio in dry refluxing ethanol. All the isolated complexes have the general composition [M(L)(A)]. The plausible structure of these newly synthesized complexes has been proposed on the basis of elemental analyses, molar conductances, molecular weight measurement, and various spectral (IR, ¹H NMR, and ¹³C NMR) studies, and four coordinated geometries have been assigned to these complexes. All the complexes and ligands have been screened for their antibacterial activity.     

Fluorescence signaling of aromatic oxoanion inclusion within metal-ion activated molecular receptor complexes formed from 2-(9-anthracenylmethylamino)ethyl-appended cyclen

Our observations that 1-[2-[(9-anthracenylmethylamino)ethyl)-4,7,10-tris[(2S)-2-hydroxy-3-phenoxypropyl]-1,4,7,10-tetraazacyclododecane, L¹, complexes Cd(II) to form fluorescent [CdL¹]²⁺ which undergoes a fluorescence change when it acts as an aromatic anion receptor complex has caused us to explore further the potential development of an interesting sequestration/sensor system. Accordingly, three new, octadentate, fluorescent, macrocyclic ligands, 1-[2-[(9-anthracenylmethyl)((2S)-2-hydroxy-3-phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L²), 1-[2-[(9-anthracenyl-methyl)((2S)-2-hydroxy-3-(4??-methyl)phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-(4??-methyl)phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L³), and 1-[2-[(9-anthracenylmethyl)((2S)-2-hydroxy-3-(4??-t-butyl)phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-(4??-t-butyl)phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L⁴), have been prepared with a view to using their metal complexes to study aromatic anion sequestration. The eight-coordinate Cd(II) complexes of L² and L³, [CdL²](ClO₄)₂·5H₂O and [CdL³](ClO₄)₂·2H₂O·2Et₂O are both capable of acting as receptors for a range of aromatic oxoanions. This is demonstrated by perturbation of the anthracene derived fluorescence emission intensity as the guest aromatic oxoanion and the receptor complex combine. In 20% aqueous 1,4-dioxane the receptor complex/aromatic oxoanion association constants are in the range of 10^3.2 M^?1 (guest = p-hydroxybenzoate) to 10^7.3 M^?1 (guest = 3,4,5-trihydroxybenzoate).     

Synthesis and crystal structure of Mn(II) complexes with novel macrocyclic Schiff-base ligands containing piperazine moiety

A series of Mn(II) macrocyclic Schiff-base complexes [MnLⁿCl]⁺ (n = 1–4) have been prepared via the Mn(II) templated [1+1] cyclocondensation of 2,6-diacetylpyridine or 2,6-pyridinedicarbaldehyde with the symmetrical 1,4-bis(3-aminopropyl)piperazine or the novel asymmetrical N,N′(2-aminoethyl)(3-aminopropyl)piperazine linear amines containing piperazine moiety. The complexes have been characterized by elemental analyses, IR, FAB-MS, magnetic studies and conductivity measurements. The crystal structure of [MnL²(CH₃OH)Cl](ClO₄) and [MnL⁴Cl](PF₆) complexes have also been determined showing the metal ion in a N₄OCl pentagonal bipyramidal or N₄Cl highly distorted octahedral geometry, respectively.     

5′-DEOXYADENOSINE COMPLEXES WITH DIVALENT 3d METAL PERCHLORATES

Abstract

5′-deoxyadenosine (LH) complexes with divalent 3d metal perchlorates were prepared by refluxing mixtures of LH and salt in triethylorthoformate-ethylacetate. With one exception (M = Co), adducts of the types M(LH)₂(ClO₄)₂.3EtOH (M = Mn, Fe, Ni, Zn) and Cu(LH)₃(ClO₄)₂.EtOH were obtained. Ethanol is introduced to the system by hydrolysis of triethylorthoformate during the dehydration of the metal salts. Co(II) perchlorate yielded a complex involving both neutral LH and monoanionic L^? ligands, i. e., Co₂(LH)L₂(ClO₄)₂.4EtOH. An analogous Cu(II) complex, Cu₂(LH)L₂(ClO₄)₂.EtOH.3H₂O, was also obtained by refluxing substantially more dilute suspensions of LH and Cu salt, relative to the standard preparative method employed. The new complexes were characrerized as dimers or linear polymers, involving bridging bidentate N1,N7-bound LH ligands between adjacent metal ions and coordination number six. The new adducts also involve terminal N7-bound LH and EtOH ligands and ionic perchlorate, and the Co and Cu complexes a chelating N6,N7-bound L^? (monodeprotonation of the exocyclic NH₂ group) per metal ion and terminal -OClO₃ and ROH (R = Et or H) ligands.     

Tetranuclear Zn(II) complexes with compartmental and dicyanamido ligands: synthesis,structure, and luminescent properties

New tetranuclear compounds have been obtained by reacting binuclear complexes, [Zn₂L ⁿ (μ-OH)(H₂O)₂](ClO₄)₂, with sodium dicyanamide (HL ⁿ are end-off bicompartmental ligands resulting from condensation between 2,6-diformyl-p-cresol with N,N-dimethyl-ethylenediamine or 2-aminomethyl-pyridine). The complexes, [{L¹(μ-OH)Zn₂}(μ _1,5-dca)₂{Zn₂(μ-OH)L¹}](ClO₄)₂ (1) and [{Zn₂L²(μ ₃-OH)(dca)}₂](ClO₄)₂?·?2H₂O (2), have been characterized by single-crystal X-ray diffraction. The angular nature of the bridging dicyanamido induces the “M” shape of the tetranuclear cationic unit in 1. The tetranuclear cation, because of its particular shape, acts as a receptor toward one perchlorate ion, which is hydrogen bonded to the hydroxo groups. This tetranuclear unit in 2 has a defective heterocubane structure. The luminescence properties of the new tetranuclear complexes have been investigated.     

Heterodinukleare Cobalt(II)‐, Nickel(II)‐, Kupfer(II)‐, Zink(II)und Palladium(II)‐Komplexe mit einem makrocyclischen Liganden vom Schiff‐Basen‐Typ: Synthesen und Strukturen

Complexes with Macrocyclic Ligands. IV. Heterodinuclear Cobalt(II), Nickel(II), Copper(II), Zinc(II) and Palladium(II) Complexes with a Macrocyclic Ligand of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of nickel(II), copper(II), and palladium(II) complexes, [ML^Ph] ( 3 ; L^Ph = N,N′‐phenylene‐bis(3‐formyl‐5‐tert.‐butyl‐salicylaldimine)), are described. These neutral mononuclear complexes react with metal(II) perchlorate and 1,3‐propylenediamine to form heterodinuclear, macrocyclic, cationic complexes of the type [MM′(L^Ph,3)]²⁺ ( 4 ; M = Ni, Cu, Pd; M′ = Co, Cu, Zn). The structures of the five new compounds [NiCo(L^Ph,3)](ClO₄)₂, [NiCu(L^Ph,3)](ClO₄)₂, [CuCu(L^Ph,3)](ClO₄)₂, [CuZn(L^Ph,3)](ClO₄)₂, and [PdCu(L^Ph,3)](ClO₄)₂ were determined by X‐ray diffraction.