Magnetic behavior in solids and films of the Prussian blue structured materials

Chapter 1 introduces the concept of molecule-based magnets and a class of compounds related to Prussian blue that are targeted as magnetic materials. Basic concepts of magnetism and a super exchange model for magnetic exchange in the Prussian blue-like compounds are introduced.; Chapter 2 describes the synthesis and characterization of {dollar}rm lbrack Mnsp{lcub}IV{rcub}(CN)sb6rbrack sp{lcub}2-{rcub}{dollar}. Due to the hydrolytic instability of {dollar}lbrackrm Mnsp{lcub}IV{rcub}(CN)sb6rbrack sp{lcub}2-{rcub}{dollar} nonaqueous synthetic routs to this complex are pioneered. This anion is made in high yield and shown to be well behaved in nonaqueous media.; In Chapter 3 two previously unknown compounds, {dollar}rm lbrack Csb{lcub}12{rcub}Nsb{lcub}12{rcub}rbrack sp{lcub}2-{rcub}{dollar} and {dollar}rm lbrack Mnsp{lcub}II{rcub}(CN)sb4rbrack sp{lcub}2-{rcub}{dollar}, are structurally and spectroscopically characterized. The {dollar}rm lbrack Mnsp{lcub}II{rcub}(CN)sb4rbrack sp{lcub}2-{rcub}{dollar} ion is produced both photochemically and thermochemically from {dollar}rm lbrack Mnsp{lcub}IV{rcub}(CN)sb6rbrack sp{lcub}2-{rcub}{dollar}. Photolysis of {dollar}rm lbrack Mnsp{lcub}IV{rcub}(CN)sb6rbrack sp{lcub}2-{rcub}{dollar} in dichloromethane solution leads to the formation of {dollar}rm lbrack Csb{lcub}12{rcub}Nsb{lcub}12{rcub}rbrack sp{lcub}2-{rcub}{dollar}.; Chapter 4 presents the synthesis and characterization of a series of divalent metal salts. The hexakisacetonitrile adducts of V{dollar}rm sp{lcub}II{rcub}, Crsp{lcub}II{rcub}, Mnsp{lcub}II{rcub}, Fesp{lcub}II{rcub}, Cosp{lcub}II{rcub},{dollar} and {dollar}rm Nisp{lcub}II{rcub}{dollar} are combined with the weakly coordinating tetrakis(3,5-bis(trifluoromethyl)phenyl) borate anion, producing salts that are soluble in organic solvents such as tetrahydrofuran, dichloromethane, and diethyl ether.; In Chapter 5 the {dollar}rm Nilbrack Mn(CN)sb6rbrack{dollar} and {dollar}rm Colbrack Mn(CN)sb6rbrack{dollar} Prussian blue analogs are investigated. Magnetic ordering temperatures, T{dollar}rm sb{lcub}c{rcub}{dollar}, are found for these at 4.8 and {dollar}<{dollar}1.75 K, respectively, as well as structural disorder leading to unexpected spin-glass behavior.; In Chapter 6 {dollar}rm Felbrack Mn(CN)sb6rbrack ,{dollar} T{dollar}sb{lcub}rm c{rcub}{dollar} = 10.1 K, is shown to undergo linkage isomerization to {dollar}rm Mnlbrack Fe(CN)sb6rbrack .{dollar} This compound suffers from structural disorder as well and magnetic spin glass behavior is resolved.; Chapter 7 presents the magnetic behavior of {dollar}rm Mnlbrack Mn(CN)sb6rbrack ,{dollar} T{dollar}rmsb{lcub}c{rcub}{dollar} = 27.1 K, {dollar}rm Crlbrack Mn(CN)sb6rbrack ,{dollar} T{dollar}rm sb{lcub}c{rcub}{dollar} = 10.6 K, and {dollar}rm Vlbrack Mn(CN)sb6rbrack ,{dollar} T{dollar}rm sb{lcub}c{rcub}{dollar} = 19.0 K. Disorder is also prevalent in these compounds. Reentrant spin-glass behavior is resolved in Mn- and {dollar}rm Crlbrack Mn(CN)sb6rbrack ,{dollar} whereas typical spin-glass behavior is resolved for {dollar}rm Vlbrack Mn(CN)sb6rbrack .{dollar}; Chapter 8 describes the electrodeposition, structural, and magnetic properties of films (ca. 1.0 {dollar}pm{dollar} 0.5 {dollar}mu{dollar}m thick) based on the {dollar}rm Ksb{lcub}n{rcub}Crsb{lcub}x{rcub}lbrack Cr(CN)sb6rbrack sb{lcub}y{rcub}{dollar} Prussian blue analog. Magnetic ordering temperatures of the films can be varied between 135 and 260 K as a function of oxidation state. Coercive behavior is strongly dependent upon oxidation state as well as film morphology.; Chapter 9 contains the refinement details, positional parameters, bond distances, bond angles, and general displacement parameters for the single crystal studies of {dollar}rm lbrack (Phsb3P)sb2Nrbrack sb3lbrack Mn(CN)sb6rbrack, lbrack (Phsb3P)sb2Nrbrack 2lbrack Csb{lcub}12{rcub}Nsb{lcub}12{...