High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

Études spectroscopiques expérimentales et théoriques de complexes de métaux de transition

Cette thèse présente une série d'études qui visent la compréhension de la structure électronique de complexes de métaux de transition en employant diverses méthodes de spectroscopie. L'information sur la structure électronique aide à comprendre et développer des nouveaux matériaux, des nouvelles voies de synthèses, ainsi que des nouveaux modèles théoriques. Habituellement, afin d'explorer la structure électronique d'un système qui comporte en son centre un métal de transition, l'information fournie par les spectres d'un seul composé n'est pas suffisante. On étudie une série de composés similaires, qui ont le même métal de transition à un degré d'oxydation donné, ainsi que des ligands qui forment des liaisons de différentes forces et caractéristiques avec le métal. Cependant, ces changements, bien qu'on les désire de faible impact, créent une grande perturbation de la structure électronique visée par les études. Afin d'étudier en profondeur une seule structure électronique, nous employons une stratégie d'analyse moins perturbante. Nous appliquons une pression hydrostatique sur les complexes de métaux de transition. Cette pression perturbe le système suffisamment pour nous livrer davantage d'informations sur la structure électronique, sans la « dénaturer ». Afin d'étudier précisément ces systèmes perturbés, la technique d'application de pression est conjuguée, dans la littérature, aux diverses techniques de spectroscopie d'absorption UV-visible, de luminescence, ainsi que de diffusion Raman. Pour extraire un maximum d'informations de ces expériences, on emploie des techniques de calculs de structure électronique ainsi que de dynamique des noyaux. Dans cette thèse, on tente de mettre en lumière la structure électronique de composés de molybdène(IV), de platine(II) et palladium(II) à l'aide de la technique de pression couplée aux spectroscopies de luminescence et de diffusion Raman. Dans le chapitre 3, on observe un déplacement de la bande de luminescence de +12 cm-1/kbar entre la pression ambiante et 25 kbar pour le complexe trans-[MoOCl(CN-t-Bu)4]BPh4, dont le centre métallique molybdène(IV)est de configuration électronique 4d2. Il s'agit de la première variation positive observée pour un complexe de type métal-oxo. À des pressions plus élevées, la tendance s'inverse. Le maximum d'énergie de la bande de luminescence se déplace de -8 cm-1/kbar. Ce changement de variation présage d'une compétition interne entre les ligands situés sur les différents axes de l'octaèdre. À l'aide de calculs basés sur la théorie de la fonctionnelle de la densité, on propose un mécanisme pour expliquer ce phénomène. Au cours du chapitre 4, on étudie des complexes de palladium(II) et de platine(II) qui ont les mêmes ligands. Un de ces ligands est le 1,4,7-trithiacyclononane (ttcn). On constate qu'à basse pression le ligand est bidentate. Par contre, lorsque la pression augmente, on constate, par exemple à l'aide du complexe [Pt(ttcn)Cl2], qu'une interaction anti-liante supplémentaire se produit entre le ligand ttcn et le métal, ce qui change la nature de l'orbitale HOMO. On observe un déplacement de la bande de luminescence de -19 cm-1/kbar. Tel que pour le complexe de molybdène(IV), le déplacement de la bande de luminescence dépend de la compétition entre les ligands situés sur les différents axes de l'octaèdre. L'interaction liante entre l'ion platine(II) et l'atome de soufre axial est l'effet le plus plausible qui peut induire un déplacement de la bande de luminescence vers les basses énergies. Ceci nous indique que cette interaction domine. Par contre, pour ce qui est du complexe palladium(II), la compétition est remportée par d'autres effets, car le déplacement de la bande de luminescence est de +6 cm-1/kbar. Encore une fois, des calculs, basés sur la théorie de la fonctionnelle de la densité, aident à explorer les causes de ces observations en suggérant des explications corroborées simultanément par les diverses expériences de spectroscopie. Lors du chapitre 5, une étude plus exacte de la structure électronique ainsi que de la dynamique des noyaux de complexes de métaux de transition est présentée. En effet, les complexes de palladium(II) et de platine(II), de type [M(X)4]2-, ont une structure simple, très symétrique. Le premier état excité de ces molécules subit la distorsion Jahn-Teller. On veut établir un protocole de travail pour les expérimentateurs afin d'analyser des spectres de molécules pour lesquelles l'approximation de Born-Oppenheimer n'est pas valide. On utilise la théorie de la fonctionnelle de la densité dépendante du temps ainsi que le modèle de Heidelberg afin de décrire des effets non adiabatique. On tente d'établir l'influence des effets non adiabatiques sur les spectres de ce type de complexe.

Synthesis, characterization and chromotropism properties of Ni(II) complexes featuring diphenyl(dipyrazolyl) methane

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Studies On Supported Cobalt (Ii), Nickel (Ii) and Copper (Ii) Complexes Of O-Phenylenediamine and Schiff Bases Derived from 3-Hydroxyquinoxaline-2-Carboxaldehyde

The thesis deals with the synthesis, characterization and catalytic activity studies of supported cobalt(ii), nickel(II) and copper(II) complexes of O-phenylenediamine and Schiff bases derived from 3-hydroxyquinoxaline -2-carboxaldehyde. Zeolite encapsulation and polymer anchoring was employed for supporting the complexes. The characterization techniques proved that the encapsulation as well as polymer supporting has been successfully achieved. The catalytic activity studies revealed that the activities of the simple complexes are improved upon encapsulation. Various characterization techniques are used such as, chemical analysis, EPR, magnetic measurements, FTIR studies, thermal analysis, electronic spectra, XRD, SEM, surface area, and GC.The present study indicated that the that the mechanism of oxidation of catechol and DTBC by hydrogen peroxide is not altered by the change in the coordination sphere around the metal ion due to encapsulation. This fact suggests outer sphere mechanism for the reactions. The catalytic activity by zeolite encapsulated complex was found to be slower than that by the neat complex. The slowing down of the reaction in the zeolite case is probably due to the constraint imposed by the zeolite framework. The rate of DTBC ( 3,5-di-tert-butylchatechol)oxidation was found to be greater than the rate of catechol oxidation. This is obviously due to the presence of electron donating tertiary butyl groups.

Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene

Co(II), Ni(II) and Cu(II) complexes of dimethylglyoxime and N,N-ethylenebis(7-methylsalicylideneamine) have been synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. The hybrid materials obtained have been characterized by elemental analysis, SEM, XRD, surface area, pore volume, magnetic moment, FTIR, UV-Vis and EPR techniques. Analysis of data indicates the formation of complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activities for hydrogen peroxide decomposition and oxidation of benzyl alcohol and ethylbenzene of zeolite complexes are reported. Zeolite Cu(II) complexes were found to be more active than the corresponding Co(II) and Ni(II) complexes for oxidation reactions. The catalytic properties of the complexes are influenced by their geometry and by the steric environment of the active sites. Zeolite complexes are stable enough to be reused and are suitable to be utilized as partial oxidation catalysts.

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

Cobalt (II), Nickel (II), and Copper (II) Complexes of Polystyrene-Supported Schiff Bases

Two novel polystyrene-supported Schiff bases, PSOPD and PSHQAD, were synthesized. A polymerbound aldehyde was condensed with o-phenylenediamine to prepare the Schiff base PSOPD, and a polymer-bound amine was condensed with 3-hydroxyquinoxaline-2-carboxaldehyde to prepare the Schiff base PSHQAD. This article addresses the study of cobalt (II), nickel (II), and copper (II) complexes of these polymer-bound Schiff bases. All the complexes were characterized, and the probable geometry was suggested using elemental analysis, diffuse reflectance ultraviolet, Fourier transform infrared spectroscopy, thermal studies, surface area studies, and magnetic measurements.

Copper(II) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde: Crystal structure of a binuclear complex

Ten copper(II) complexes {[CuL1Cl] (1), [CuL1NO3]2 (2), [CuL1N3]2 · 2/3H2O (3), [CuL1]2(ClO4)2 · 2H2O (4), [CuL2Cl]2 (5), [CuL2N3] (6), [Cu(HL2)SO4]2 · 4H2O (7), [Cu(HL2)2] (ClO4)2 · 1/2EtOH (8), [CuL3Cl]2 (9), [CuL3NCS] · 1/2H2O (10)} of three NNS donor thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-(methyl), N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of compound 9 has been determined by X-ray diffraction studies and is found that the dimer consists of two square pyramidal Cu(II) centers linked by two chlorine atoms.

Studies on the preparation of Supported nickel catalysts using bis(ethylenediamine)nickel(II) complexes as precursors

Dept.of Applied Chemistry,Cochin University of Science and Technology

The ligating versatility of halides and pseudohalides in copper(II) complexes- monomers, dimers and chains”

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2008-2013. The thesis brings to light, our attempts to evaluate the coordination behavior of some compounds of interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are well-authenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of copper complexes with halides and pseudohalides. In addition to single crystal X-ray diffraction studies, various physico-chemical methods of analysis were also used for the characterization of the complexes

Copper(II) complexes derived from di-2-pyridyl ketone-N4-phenyl-3-semicarbazone: Synthesis and spectral studies

Five copper(II) complexes [CuLCl]2·CuCl2·4H2O (1), [CuLOAc] (2), [CuLNO3]2 (3), [CuLN3] (4) and [CuLNCS]·3/2H2O (5) of di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL) were synthesized and characterized by elemental analyses and electronic, infrared and EPR spectral techniques. In all these complexes the semicarbazone undergoes deprotonation and coordinates through enolate oxygen, azomethine and pyridyl nitrogen atoms. All the complexes are EPR active due to the presence of an unpaired electron. EPR spectra of all the complexes in DMF at 77K suggest axial symmetry and the presence of half field signals for the complexes 1 and 3 indicates dimeric structures

Preparation, magnetic and EPR spectral studies of copper(II) complexes of an anticancer drug analogue

Ten new copper(II) complexes of five potential bisthiocarbohydrazone and biscarbohydrazone ligands were synthesized and physico-chemically characterized. The spectral and magnetic studies of compounds are consistent with the formation of asymmetric di-, tri- or tetranuclear copper(II) complexes of deprotonated forms of respective ligands. The variable temperature magnetic susceptibility measurements of all complexes showantiferromagnetic interactions between the Cu(II) centers, in agreement with very broad powder EPR spectra. However, frozen solution EPR spectral studies are found in contradiction with the solid-state magnetic studies and indicate that the complexes are not very stable in solutions; the possible fragmentations of complexes are found in agreement with MALDI MS results. The EPR spectral simulation of most of the compounds is in agreement with the presence of two uncoupled Cu(II) species in solution.

Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone

An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2] H2O (1), [CuLNCS] ½H2O (2), [CuLNO3] ½H2O (3), [Cu(HL)Cl2] H2O (4), [Cu2(HL)2(SO4)2] 4H2O (5), [CuLClO4] ½H2O (6), [CuLBr] 2H2O (7), [CuL2] H2O (8) and [CuLN3] CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2 y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure

Syntheses, EPR spectral studies and crystal structures of manganese(II) complexes of neutral N,N donor bidentate Schiff bases and azide/thiocyanate as coligand

Four manganese(II) complexes Mn2(paa)2(N3)4 (1), [Mn(paa)2(NCS)2] 3/2H2O (2), Mn(papea)2(NCS)2 (3), [Mn(dpka)2(NCS)2] 1/2H2O(4) of three neutral N,N donor bidentate Schiff bases were synthesized and physico- chemically characterized by means of partial elemental analyses, electronic, infrared and EPR spectral studies. Compounds 3 and 4 were obtained as single crystals suitable for X-ray diffraction. Compound 4 recrystallized as Mn(dpka)2(NCS)2. Both the compounds crystallized in the monoclinic space groups P21 for 3 and C2/c for 4. Manganese(II) is found to be in a distorted octahedral geometry in both the monomeric complexes with thiocyanate anion as a terminal ligand coordinating through the nitrogen atom. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines and the zero field splitting parameters (D and E) were calculated.

Copper(II) complexes of mono-anionic glutamate: anionic influence in the variations of molecular and supramolecular structures

Three new polynuclear copper(II) complexes of singly deprotonated L-glutamic acid (L-glu), {[Cu(bipy)(2)][Cu(bipy)(L-glu)H2O](2)(BF4)(4)center dot(H2O)(3)}(n) (1), {[Cu(bipy)(L-glu)H2O][Cu(bipy)(L-glu)(ClO4)]( ClO4)center dot(H2O)(2)}(n) ((2)) and [Cu(phen)(L-glu)H2O](2)(NO3)(2)center dot(H2O)(4) (3) (bipy = 2,2-bipyridine, phen = 1,10-phenanthroline), were synthesized in acidic pH (ca. 2.5) and characterized structurally. In all the complexes, L-glutamic acid acts as a bidentate chelating ligand, leaving the protonated carboxylic acid free. Both in 1 and 2, two different types of species [Cu(bipy)(2)](BF4)(2) and [Cu(bipy)(L-glu)H2O] BF4 for 1 and [Cu(bipy)(L-glu)H2O]ClO4 and [Cu(bipy)(L-glu)(ClO4)] for 2 coexist in the solid state. In complex 1, the [C( bipy)(L-glu)H2O]+ units are joined together by syn-anti carboxylate bridges to form an enantiopure (M) helical chain and the [Cu(bipy)(2)](2+) presents a very rare example of the four-coordinate distorted tetrahedral geometry of Cu(II). In complex 2, the [Cu(bipy)(L gluClO(4))] units are joined together by weakly coordinating perchlorate ions to form a 1D polymeric chain while the [Cu(bipy)(L-glu)H2O]+ units remain as mononuclear species. The different coordinating ability of the two counter anions along with their involvement in the H-bonding network seems likely to be responsible for the difference in the final polymeric structures in the two compounds. Variable-temperature (2-300 K) magnetic susceptibility measurements show negligible coupling for both the complexes. The structure of 3 consists of two independent monomeric [Cu(phen)(L-glu)H2O]+ cations, two nitrate anions and four water molecules. The copper atom occupies a five-coordinate square pyramidal environment with a water molecule in the axial position.