0000000001306819
AUTHOR
Augustin M. Madalan
Self-ordering of metallogrid complexes via directed hydrogen-bonding.
Reaction of imidazole aldehydes with dihydrazino derivatives of 2-phenylpyrimidine provides a family of bis(acylhydrazone) ligands which form [2 × 2] metallogrid complexes with transition metal ions including Fe(II), Co(II), Cu(II) and Zn(II). The free ligands show H-bonding interactions, both donor and acceptor, largely involving the imidazole units, while binding of the metal ions occupies all the acceptor sites and leaves only the pyrrolic-NH site as an H-bond donor, although its deprotonation by a strong base can regenerate an acceptor. These H-bonding interactions have been studied by (1)H NMR spectroscopy in solution and in the solid state by means of several crystal structure determi…
Generation of [2×2] Grid Metallosupramolecular Architectures from Preformed Ditopic Bis(acylhydrazone) Ligands and through Component Self‐Assembly
Ditopic bis(acylhydrazone) ligands, derived from the reactions of carbohydrazides with 2-phenylpyrimidine-4,6-dicarbaldehyde and designed for grid formation with octahedrally coordinating transition-metal ions, exhibit a varied coordination chemistry depending upon the degree of their deprotonation. The neutral acylhydrazones are relatively poor ligands and are seemingly involved in multiple, labile complexation equilibria varying with the solvent and the particular metal salt in solution; nevertheless, grid complexes of different forms can be isolated in the solid state. Although only limited study has been made of the singly deprotonated ligands, grid species appear to be much more readil…
A new mixed-valence hexanuclear cobalt complex, [Co4IICo2III(dea)2(Hdea)4)(piv)4](ClO4)2·H2O: Synthesis, crystal structure and magnetic properties
A new Co II /Co III hexanuclear complex, [Co 4 II Co 2 III (dea) 2 (Hdea) 4 )(piv) 4 ](ClO 4 ) 2 ·H 2 O 1 , has been obtained by reacting cobalt(II) perchlorate, diethanolamine, and pivalic acid (H 2 dea = diethanolamine and piv = pivalato anion). The cobalt ions are held together by four μ 3 and four μ 2 alkoxo bridges as well as by four syn – syn carboxylato groups. The hexanuclear motif contains four Co(II) and two Co(III) ions. The {Co II 4 Co III 2 (μ 2 -O) 4 (μ 3 -O) 4 } core can be described as a four face-sharing monovacant and bivacant distorted heterocubane units. The cobalt(III) ions are hexacoordinated. Two of the cobalt(II) are hexacoordinated, while the two others are pentacoo…
Structural and metallo selectivity in the assembly of [2 × 2] grid-type metallosupramolecular species: Mechanisms and kinetic control
An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L(2)](+) complex which can be used as a "corner" species for the "Coupe du Roi" assembly of trans,trans-[Co(2)M(2)L(4)](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 × 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn(4)L(4)](CF(3)SO(3))(8)·4CH(3)CN cry…
Heterometallic CoII-CoIII-MII alkoxido-bridged heptanuclear motifs (M = Cu, Zn). Syntheses, crystal structures and magnetic properties
Two new alkoxido-bridged heterometallic complexes of formula [CoIICoIII 3CuII 3(dea)6(CH3COO)3](ClO4)0.75(CH3COO)1.25 (1) and [CoII 2CoIII 2ZnII 3(tea)2(piv)6(CH3O)2(OH)2(CH3OH)2]·H2O 2 (H2dea=diethanolamine, H3tea=triethanolamine and Hpiv=pivalic acid) have been assembled using aminoalcohol ligands. The cationic core in 1 possesses a threefold crystallographic axis, and it exhibits a set of three copper(II), one cobalt(II) and three cobalt(III) ions arranged as a hexagon of alternating copper(II) and cobalt(III) ions around the central cobalt(II) ion. Each edge of the hexagon is defined by a double alkoxido bridge, the outer one being bis-monodentate with copper(II)-cobalt(III) pair wherea…
Mononuclear Fe(III) and tetranuclear [Fe(III)Gd(III)]2 complexes with a Schiff-base ligand derived from the o-vanillin: Synthesis, crystal structures and magnetic properties
The mononuclear high-spin iron(III) complexes [Fe(3-MeOsalpn)Cl(H 2 O)] ( 1 ) and [Fe(3-MeOsalpn)(NCS)(H 2 O)]·0.5CH 3 CN ( 2 ) and the tetranuclear oxo-bridged compound [{Fe(3-MeOsalpn)Gd(NO 3 ) 3 } 2 (μ-O)]·CH 3 CN ( 3 ) [3-MeOsalpn 2− = N , N ′-propylenebis(3-methoxysalicylideneiminate)] have been prepared and magneto-structurally characterised. The iron(III) ion in 1 and 2 is six-coordinated in a somewhat distorted octahedral surrounding with the two phenolate-oxygens and two imine-nitrogens from the Schiff-base building the equatorial plane and a water ( 1 and 2 ) and a chloro ( 1 )/thiocyanate-nitrogen ( 2 ) in the axial positions. The neutral mononuclear units of 1 and 2 are assemb…
Radical cation salts of BEDT-TTF, enantiopure tetramethyl-BEDT-TTF, and TTF-Oxazoline (TTF-Ox) donors with the homoleptic TRISPHAT anion
International audience; The synthesis and crystal structures of five radical cation salts based on the organic donors bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), racemic ethylenedithio-methyl-oxazoline-tetrathiafulvalene (EDT-TTF-MeOx) and the enantiopure (S,S,S,S) and (R,R,R,R) tetramethyl-bis(ethylenedithio)tetrathiafulvalene (TMBEDT-TTF) and the D3-symmetric anion tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) are reported. The salts are formulated as [BEDT-TTF][(rac)-TRISPHAT]·CH2Cl2 (1), [BEDT-TTF][(rac)-TRISPHAT]·2CH3CN (2), [(rac)-EDT-TTF-Ox][(rac)-TRISPHAT]·CH3CN (3), [(S,S,S,S)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (4), and [(R,R,R,R)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (…
C3-symmetric trinuclear copper(ii) species as tectons in crystal engineering
Three new complexes have been obtained using C3-symmetric trinuclear complexes as tectons; [Cu3(felden)(NCS)3(dmf)3] (1), [Cu3(felden)(mand)3]·(C2H5)2O (2), and [Cu3(felden)(dca)3(C2H5OH)]·2H2O (3) (H3felden is the Schiff base resulting from the condensation of 2,4,6-triformylphloroglucinol with N,N-dimethylethylenediamine, mand− is the anion of the R-mandelic acid and dca− is the dicyanamide anion). Compounds 1 and 2 are discrete trinuclear species, while compound 3 is a 2D coordination polymer, constructed from trinuclear nodes and dicyanamido spacers. The variable-temperature magnetic properties of 1–3 have been investigated and they reveal the occurrence of weak antiferromagnetic intera…
New complexes of Ni(II) and Co(III) with a Schiff-base ligand derived from o -vanillin. Crystal structure, magnetic and catalytic properties of a dissymmetric binuclear nickel(II) complex
Abstract A binuclear complex, [Ni2L2(NO3)(H2O)(CH3CN)]ClO4·CH3CN (1), has been obtained using a Schiff-base ligand (HL) derived from o-vanillin and 4-(2-aminoethyl)morpholine. The crystal structure of 1 has been solved. Both Ni(II) ions are hexacoordinated, but they display different coordination spheres. The exchange interaction between the two nickel ions is antiferromagnetic (J = −7.9 ± 0.2 cm−1; H = −JS1S2), in line with the DFT calculations. Compound 1 has been tested as a catalyst in the epoxidation of various olefins. The reaction of the same ligand with a mixture of cobalt(II) perchlorate and nitrate affords a mononuclear Co(III) complex, [CoL2(H2O)]ClO4·CH3OH (2).
Two-Dimensional Coordination Polymers Constructed Using, Simultaneously, Linear and Angular Spacers and Cobalt(II) Nodes. New Examples of Networks of Single-Ion Magnets
Two novel bidimensional coordination polymers, [Co(azbbpy)(4,4'-bipy)0.5(DMF)(NCS)2]·MeOH (1) and [Co(azbbpy)(bpe)0.5(DMF)(NCS)2]·0.25H2O (2), resulted from the assembling of cobalt(II) ions by 1,3-bis(4-pyridyl)azulene, using either 4,4'-bipyridyl or 1,2-bis(4-pyridyl)ethylene as neutral spacers. The cobalt(II) nodes in 1 and 2 act as single-ion magnets (SIMs).
[W(bipy)(CN)6]−: A Suitable Metalloligand in the Design of Heterotrimetallic Complexes. The First CuIILnIIIWV Trinuclear Complexes
The first 3d-4f-5d heterotrimetallic complexes using [W(V)(bipy)(CN)(6)](-) as a metalloligand were synthesized (bipy = 2,2'-bipyridine). The structural and magnetic properties of three [Cu(II)Ln(III)W(V)] complexes (Ln = Gd, Ho, Tb) are discussed.
One-dimensional coordination polymers constructed from di- and trinuclear {3d–4f} tectons. A new useful spacer in crystal engineering: 1,3-bis(4-pyridyl)azulene
Four new heterometallic 3d–4f complexes have been obtained using bi- and trinuclear building blocks: 1∞[Ni(L1)Gd(NO3)3(azbbpy)]·CH3CN (1), [Zn(L1)Eu(NO3)3(azbbpy)]·H2O (2), 1∞[(CuL2)2Gd(NO3)2(dca)] 3 and 1∞[(NiL2)2Dy(H2O)4(oxy-bbz)]NO3·3H2O (4), [H2L1 = 1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol), H2L2 = 2,6-di(acetoacetyl)pyridine, azbbpy = 1,3-bis(4-pyridyl)azulene, dca− = dicyanamide anion, and oxy-bbz = the dianion of the 4,4′-oxy-bis(benzoic) acid]. 1 and 2 represent the first complexes containing 1,3-bis(4-pyridyl)azulene as a ligand. 1, 3, and 4 are one-dimensional coordination polymers constructed from heterometallic nodes connected by the exo-dentate ligands. Helical chai…
CCDC 1550041: Experimental Crystal Structure Determination
Related Article: Eliza Martin, Violeta Tudor, Augustin M. Madalan, Catalin Maxim, Floriana Tuna, Francesc Lloret, Miguel Julve, Marius Andruh|2017|Inorg.Chim.Acta|475|98|doi:10.1016/j.ica.2017.05.077
CCDC 949950: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Catalin Maxim, Miguel Julve, Francesc Lloret, Marius Andruh|2014|CrystEngComm|16|319|doi:10.1039/C3CE41592A
CCDC 949949: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Catalin Maxim, Miguel Julve, Francesc Lloret, Marius Andruh|2014|CrystEngComm|16|319|doi:10.1039/C3CE41592A
CCDC 1029369: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Sergiu Shova, Julia Vallejo, Miguel Julve, Francesc Lloret, Marius Andruh|2015|Inorg.Chem.|54|16|doi:10.1021/ic5025197
CCDC 949948: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Catalin Maxim, Miguel Julve, Francesc Lloret, Marius Andruh|2014|CrystEngComm|16|319|doi:10.1039/C3CE41592A
CCDC 1029370: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Sergiu Shova, Julia Vallejo, Miguel Julve, Francesc Lloret, Marius Andruh|2015|Inorg.Chem.|54|16|doi:10.1021/ic5025197
CCDC 1550042: Experimental Crystal Structure Determination
Related Article: Eliza Martin, Violeta Tudor, Augustin M. Madalan, Catalin Maxim, Floriana Tuna, Francesc Lloret, Miguel Julve, Marius Andruh|2017|Inorg.Chim.Acta|475|98|doi:10.1016/j.ica.2017.05.077
CCDC 949947: Experimental Crystal Structure Determination
Related Article: Adrian E. Ion, Simona Nica, Augustin M. Madalan, Catalin Maxim, Miguel Julve, Francesc Lloret, Marius Andruh|2014|CrystEngComm|16|319|doi:10.1039/C3CE41592A