Organic open-shell materials, which are responsive to external stimuli; such as light, electronic field, magnetic field, etc., are subject to intensive studies in recent years for their potential application in the field of organic solar cells, semiconductors, supercapacitors, singletission, non-linear optical (NLO), spintronics, and magnetic materials. As the materials with an open-shell diradical (two unpaired electrons) or polyradical (multiple unpaired electrons) character have a significant promise for next-generation optoelectronics, magnetic, and spintronic devices, it is of paramount importance to design suitable materials with tunable electronic properties. Also, a proper understanding of the molecular topology with electro-magnetic properties and correlate with quantum functionalities can move forward the field of organic photovoltaics and optoelectronics. Here, we show that controlling the radical character based on the different molecular scaffolds can lead to materials from closed-shell (all electrons are paired) low-spin (singlet state) to intermediate open-shell (multi)radical state to high-spin (triplet state) ground-state in the pristine form. In this regard, several organic donoreptor (D-A) polymeric and small molecular systems are designed and characterized. We find that the diradical character is ubiquitous in the narrow bandgap organic materials. Based on this design rule, we have reported open-shell dyes for dye-sensitized solar cells (DSCs), which show significantly red-shifted absorption in the NIR than the closed-shell counterpart dyes. Our work on the alternating D-A polymers indicate stabilization of the high-spin triplet ground-state in the neutral form, not reported for D-A type polymers. A significant delocalization of the unpaired electrons provides thermodynamic stability of the polymer, which when used in supercapacitors, a best-in-class energy density, and a long cycle life are observed. Also, we find that the spin topology can be modulated by careful selection of molecular scaffold in the extended pi-conjugated D-A polymers. Furthermore, our study on D-A macrocycles indicates that the antiferromagnetic (AFM) couplings between the unpaired electrons can be tuned by thiophene pi-spacer, developing a record polyradical character in the macromolecular systems.

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The work presented herein describes efforts to synthesize and characterize cyanide-bridged molecular compounds with high-spin ground states. This investigation focused primarily on the assembly of hexacyanometallate units with convergent cationic metal complexes that are coordinated to capping ligands. In this manner, a family of related compounds was developed that serve as models for understanding the role of magnetic exchange interactions and anisotropy in nanomagnetic materials. The work presented in Chapter II describes the successful incorporation of the [Fe(CN)6]3- building block into planar geometries with nuclearities ranging from three to ten metal centers. In Chapter III, this methodology was optimized to yield two pentanuclear FeIII/NiII clusters, namely, the trigonal bipyramidal unit, {[Ni(tmphen)2]3[Fe(CN)6]2}, and the extended square, {[Ni(bpy)2(H2O)][Ni(bpy)2]2-[Fe(CN)6]2}. Magnetic measurements on pure phases of these samples revealed that each system exhibits ferromagnetic coupling between the L.S. FeIII and NiII centers, but neither exhibits slow paramagnetic relaxation effects down to T=2K. In Chapter IV, this chemistry was extended to the [Mn(CN)6]3-building block in order to increase magnetic exchange coupling and anisotropy in this cluster type, efforts that resulted in the isolation of the molecule, {[Mn(tmphen)2]3[Mn(CN)6]2}. This cluster exhibits intramolecular antiferromagnetic exchange interactions between the Mn centers which lead to an S=11/2 ground state and a negative ZFS value (D=-0.348 cm-1), parameters that support the experimental observation of Single-Molecule Magnet (SMM) behavior at low temperatures. A detailed investigation of the physical and structural properties of {[Co(tmphen)2]3[Fe(CN)6]2} in Chapters V and VI led to the realization that the cluster exhibits sensitivity to temperature and humidity. The molecule exists in three different electronic isomeric forms in the solid state and undergoes a charge-transfer induced spin-transition (CTIST) under the influence of temperature. The results presented in Chapter VI describe the behavior of this same cluster in solution, the highlight of which is the discovery that water reacts with the cluster to form a fourth electronic isomer. Finally, it is described in Chapter VII that this Co/Fe trigonal bipyramidal unit can be used as a building block for systematically incorporating three metal types into a family of 1-D chain and cluster compounds.

The work presented herein describes efforts to synthesize and characterize cyanide-bridged molecular compounds with high-spin ground states. This investigation focused primarily on the assembly of hexacyanometallate units with convergent cationic metal complexes that are coordinated to capping ligands. In this manner, a family of related compounds was developed that serve as models for understanding the role of magnetic exchange interactions and anisotropy in nanomagnetic materials. The work presented in Chapter II describes the successful incorporation of the [Fe(CN)6]3- building block into planar geometries with nuclearities ranging from three to ten metal centers. In Chapter III, this methodology was optimized to yield two pentanuclear FeIII/NiII clusters, namely, the trigonal bipyramidal unit, {[Ni(tmphen)2]3[Fe(CN)6]2}, and the extended square, {[Ni(bpy)2(H2O)][Ni(bpy)2]2-[Fe(CN)6]2}. Magnetic measurements on pure phases of these samples revealed that each system exhibits ferromagnetic coupling between the L.S. FeIII and NiII centers, but neither exhibits slow paramagnetic relaxation effects down to T=2K. In Chapter IV, this chemistry was extended to the [Mn(CN)6]3-building block in order to increase magnetic exchange coupling and anisotropy in this cluster type, efforts that resulted in the isolation of the molecule, {[Mn(tmphen)2]3[Mn(CN)6]2}. This cluster exhibits intramolecular antiferromagnetic exchange interactions between the Mn centers which lead to an S=11/2 ground state and a negative ZFS value (D=-0.348 cm-1), parameters that support the experimental observation of Single-Molecule Magnet (SMM) behavior at low temperatures. A detailed investigation of the physical and structural properties of {[Co(tmphen)2]3[Fe(CN)6]2} in Chapters V and VI led to the realization that the cluster exhibits sensitivity to temperature and humidity. The molecule exists in three different electronic isomeric forms in the solid state and undergoes a charge-transfer induced spin-transition (CTIST) under the influence of temperature. The results presented in Chapter VI describe the behavior of this same cluster in solution, the highlight of which is the discovery that water reacts with the cluster to form a fourth electronic isomer. Finally, it is described in Chapter VII that this Co/Fe trigonal bipyramidal unit can be used as a building block for systematically incorporating three metal types into a family of 1-D chain and cluster compounds.

Thesis (Ph.D.)--Mississippi State University. Department of Physics and Astronomy. / Title from title screen. Includes bibliographical references.

Thesis (Ph.D.)--Mississippi State University. Department of Physics & Astronomy. / Title from title screen. Includes bibliographical references.

Herein, a series of tin and oxidovanadium complexes, as well as a hexanuclear manganese cluster, supported by the bidentate, dianionic perfluoropinacolate (pinF) ligand, {(O(C(CF3)2)2}2−, are reported. While six-coordinate SnIV-pinF complexes (2.1−2.3) were found to be spectroscopically similar to SnO2 (cassiterite), four-coordinate SnII-pinF complexes (2.4−2.5) possess low 119Sn NMR chemical shifts and remarkably high quadrupolar splitting. Additionally, the Sn(II) complexes are unusually unreactive towards both Lewis acids and bases. Computational analysis suggests that this lack of reactivity with Lewis acids arises from the energetic inaccessibility of the HOMO (5s), and the lack of reactivity with Lewis bases is due to donation into the LUMO (5px) by fluorine atoms on the ligand. Furthermore, monomeric and dimeric {VIV=O}- and {VV=O}-pinF complexes (3.1−3.4) were synthesized and characterized, including (Me4N)2[V2(O)2(μ-O)2(pinF)2] (3.3a). Complex 3.3a was found to catalyze the oxidation of several benzyl alcohols at room-temperature under ambient conditions, reproducing reactivity known for VOx surfaces and demonstrating the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones. Finally, a hexanuclear manganese cluster, {MnIII4MnIV2(pinF)6(OK(THF))4(OH)4}, abbreviated {Mn6} (4.1) which contains four-fold axial symmetry, and its oxidized analog {MnIII3MnIV3(pinF)6(OK(THF))4(OH)4}[PF6] (4.2), were prepared and characterized. High-field EPR measurements of 4.1 confirm a high spin magnetic ground state of ST = 11, corroborating the oxidation state assignments of the manganese centers. While EPR and CTM data suggest the possibility of slow magnetic relaxation for 4.1, field-dependent SQUID magnetometry reveals a lack of magnetic hysteresis, precluding the SMM behavior hypothesized for 4.1.

Le mode d’excitation collective exotique appelé chiralité a été étudié et des isomères de longue durée de vie ont été recherchés dans les noyaux ¹³⁶Nd et ¹³⁵Nd. Cinq paires de bandes Δ I=1 presque dégénérées et de même parité ont été identifiées à des spins élevés dans ¹³⁶Nd Les bandes observées ont été étudiées en utilisant la théorie de la fonctionnelle de densité covariante contrainte et rotation autour d'une axe incliné, et par un nouveau modèle de rotor plus particules développé pour décrire le couplage de particules dans quatre couches j à un rotor triaxial. Les propriétés de ces bandes doublet sont en bon accord avec les résultats des calculs théoriques. Par conséquent, l'existence de bandes chirales multiples (MχD) dans le noyau ¹³⁶Nd a été établie. Il s'agit de la première preuve expérimentale de l'existence de bandes chirales dans des noyaux pairs. Les cinq paires de bandes chirales constituent le plus grand ensablé de bandes chirales observé jusqu'à présent dans un seul noyau. De plus, le schéma de niveaux de ¹³⁶Nd a été considérablement étendu aux spins bas, moyens et très élevés. Les configurations possibles de toutes les bandes rotationnelles ont été attribuées á l'aide du modèle Nilsson-Strutinsky en rotation. La structure de ¹³⁶Nd a été clarifiée et les divers types d'excitations uni-particule et collectives ont été bien compris. Une nouvelle paire de bandes chirales á parité positive a été identifiée dans. Les caractéristiques des bandes soutiennent leur interprétation en termes de bandes chirales. Des bandes chirales à parité négative ayant été identifiées précédemment, la présence de multiple bandes chirales dans ¹³⁵Nd est ainsi établie. Les bandes chirales observées ont été étudiées en utilisant la théorie avec fonctionnelle de densité covariante contrainte et avec le modèle rotor plus particules; elles reproduisent fidèlement les données expérimentales, confirmant ainsi le phénomène MχD dans ce noyau. Les bandes chirales nouvellement observées dans ¹³⁵Nd représentent une étape importante dans la confirmation de l'existence du phénomène MχD dans les noyaux. La recherche d'états isométriques à longue durée de vie dans ¹³⁵Nd et ¹³⁶Nd a été aussi effectuée, mais n'a pas permis d'identifier de nouveaux isomères. Cependant, nous avons pu confirmer la présence des isomères déjà identifiés dans les noyaux ¹³⁸Nd, ¹³⁴Ce, ¹³⁶Pr, et ¹³⁷Pr dans nos données. / The exotic collective excitation mode called chirality has been investigated and long-lived isomers have been searched for in the ¹³⁶Nd and ¹³⁵Nd nuclei. Five pairs of nearly degenerate Δ I=1 bands with the same parity have been identified at high spins in ¹³⁶Nd. The observed bands were investigated by the constrained and tilted axis cranking covariant density functional theory and a new developed four single-j shells particle-rotor model. It was found that the properties of these doublet bands are in good agreement with results of the model calculations. Therefore, the multiple chiral doublets (MχD) phenomenon in the nucleus ¹³⁶Nd was confirmed. This was the first experimental evidence for the MχD bands in even-even nuclei. The five pairs of chiral doublet bands is the largest observed in a single nucleus until now. In addition, the level scheme of the ¹³⁶Nd has been extended significantly at low, medium, and very high spins. Possible configurations of all rotational bands have been assigned by using the cranked Nilsson-Strutinsky model. The band structure of ¹³⁶Nd was clarified and the various types of single-particle and collective excitations were well understood. A new pair of positive-parity chiral doublet bands has been identified in ¹³⁵Nd. The characteristics of the doublet bands support the chiral interpretation. Together with the previously reported negative-parity chiral doublet bands show the presence of MχD bands in ¹³⁵Nd. The observed doublet bands were compared with constrained covariant density functional theory and particle-rotor model calculations which nicely reproduce the experimental data, confirming the MχD phenomenon in this nucleus. The newly observed MχD bands in ¹³⁵Nd represent an important milestone in supporting the existence of MχD in nuclei. The search for long-lived isomeric states in ¹³⁵Nd and ¹³⁶Nd has also been performed. This did not lead to the identification of new isomers, but we could confirm the existence of the previously reported isomers in the nuclei ¹³⁸Nd, ¹³⁴Ce, ¹³⁶Pr, and ¹³⁷Pr in our data.

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No description available.