Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

Regioselective modification of galactose-containing polysaccharides in aqueous media

Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Memory mixed with desire : a preliminary study of philosophy and literature in the works of Friedrich Nietzsche and Milan Kundera

Memory Mixed with Desire: A preliminary study of Philosophy and Literature in the works of Friedrich Nietzsche and Milan Kundera Robert Spinelli Brock University, Department of Philosophy This thesis studies intertextuality in the works of Friedrich Nietzsche and Milan Kundera through the primary themes of memory and forgetting. The thesis starts with two introductory chapters that delineate memory according to Nietzsche and Kundera respectively. From here, I move into a discussion of Nietzsche's Ubermensch as an example of the type of forgetting that Nietzsche sees as a cure for the overabundance of memory that has led to Christian morality. Next, I explore the Kunderan concept of kitsch as the polar opposite of what Nietzsche has sought in his philosophy, finishing the chapter by tying the two thinkers together in a Kunderan critique of Nietzsche. The thesis ends with a chapter devoted to the Eternal Return beginning with an exegesis of Nietzsche's idea and ending with a similar exegesis of Kundera's treatment of this thought. What I suggest in this chapter is that the Eternal Return might itself be a form of kitsch even in its attempt to revalue existence.

Relationship between photoperiod, plasma concentration of ionic calcium and the histology of the prolactin-secreting cells of the rostral pars distalis of the pituitary gland, the corpuscles of stannius and the ultimobranchial gland in the goldfish, Carassius auratus L. /

The relationship between photoperiod, plasma concentration of ionic calcium and the histology of the prolactin-secreting cells of the rostral pars distalis of the pituitary gland, the Corpuscles of Stannius and the Ultimobranchial gland were investigated. Neither the plasma concentration of ionic calcium nor histologically apparent prolactin cell activity could be correlated with photoperiod. Some evidence of a photoperiodic effect on both the Corpuscles of Stannius and the Ultimobranchial gland was obtained. The expected reciprocal relationship between the activity of these glands was not obvious at the histological level . Quantitative and qualitative analysis at the light microscope level revealed, however, that the hormone prolactin-secreting eta cells of the rostral pars distalis and the hypocalcin-secreting cells of the Corpuscles of Stannius may be arranged in a lamellar pattern comprized of synchronous bands of cells in like-phase of a secretory cycle consisting of four stages - synthesis, storage, release and reorganization. Such synchronized cell cycles in these glands have not heretofore been described in literature. It is suggested that the maintenance of at least 255? of the cells in any one phase of the cycle ensures a supply of the required hormone at all times.

Breeding parameters of great cormorants (Phalacrocorax carbo carbo) at mixed species colonies on Prince Edward Island, Canada

Breeding parameters of Great Cormorants (PkaZac/iOCOfiCLX CCUibo dCUtbo) and Double-crested Cormorants (P. CLU/uXuA CMJhLtllb) were examined at two mixed species colonies at Cape Tryon and Durell Point, Prince Edward Island from 1976 to 1978. Differential access to nests at the two colony sites resulted in more complete demographic data for P. CCUibo than for P. CLUJiituA. In 1911j P. CCtfibo was present at both colonies by 21 March, whereas P. auAAJtuA did not return until 1 April and 16 April at Cape Tryon and Durell Point, respectively. Differences in the arrival chronology by individuals of each species and differences in the time of nest site occupation according to age, are suggested as factors influencing the nest site distribution of P. CXUtbo and P. aiVtituA at Cape Tryon. Forty-eight P. dOJtbo chicks banded at the Durell Point colony between 19 74 and 19 76 returned there to nest as two- to four-year olds in 19 77 and 19 78. Unmarked individuals with clutch-starts in April were likely greater than four years old as all marked two to four-year olds (with one possible exception) in 19 77 and 1978 had clutch-starts in May and June. Seasonal variation in the breeding success of P. dOJibo individuals was examined at Durell Point in 1977. Mean clutch-size, hatching success and fledging success exhibited a seasonal decline. Four- and 5-egg clutches represented the majority (75%) of all P. CCUibo clutches at Durell Point in 1977 and had the highest reproductive success (0.48 and 0.43 chicks fledged per egg laid respectively). Smaller clutches produced small broods with significantly higher chick mortality while larger clutches suffered high egg loss prior to clutch completion.

Influence of temperature and photoperiod upon ionic regulation in rainbow trout Salmo gairdneri

Interactions of photoperiod and temperature upon waterelectrolyte balance were examined in rainbow trout acclimated to six combinations of two photoperiods {18h light: 6h dark, o 6h light: l8h dark) and three temperatures (2, 10 and 18 C). The influence of temperature and photoperiod upon plasma, skeletal muscle, cardiac muscle and liver levels of sodium, potassium, magnesi.um, calcium, chloride, water content, water distribution and cellular ion concentrations was determined by a one way analysis of variance. Significant (p < 0.05 or better) temperature effects at common photoperiods were observed in 70% of the analyses performed, showing no bias toward either photoperiod. Significant photoperiod effects occured in 57% of the analyses performed at common temperatures. The influence of photoperiod was most prevalent at reduced temperatures. Potassium and magnesium appeared to be particularly thermosensitive, while sodium and calcium were the most photosensitive of the electrolytes. The ionic composition of all tissues studied were relatively thermosensitive, with liver apparently being the most sensitive. On the other hand; the ionic composition of skeletal and cardiac muscle appear to be the mos.t photosensitive of the tissues examined. Water content and distribution in skeletal muscle and liver were significantly influenced by temperature in 50% of the analyses performed showing a very strong bias toward UwinterU animals. Photoperiod effects were significant in 56% of the water parameters measured with a strong bias toward the two lower temperatures. Body weight was of significant influence in 16% of the 174 analyses performed. These data are discussed in terms of the effect of temperature upon ionregulatory mechanisms and the possible impact of photoperiod variations on endocrine systems influencing water-electrolyte metabolism.

Ionic regulation in goldfish, Carassius auratus, acclimated to constant and diurnally-cycling temperature conditions

The effects of a diurnal sine-wave temperature cycle (250 +- 5° C) on the wa terI-e etc r o1 yt est a t us 0 f gol df1' Sh , Carassius auratus, was assessed through determination of Na+, K+, Mg2+, Ca2+, Cl- and water content in plasma, Red blood cells and muscle tissue. Animals were also acclimated to o 0 0 static temperatures (20 C, 25 c, 30 C) corresponding to the high, low and mid-ooint temperatures of the cycle. All groups were sampled at 03:00, 09:00, 15:00 and 21:00 hr. Hemoglobin content and packed cell volume, as well as electrolyte and 'water levels were determined for each animal and red cell ion concentrations and ion : hemoglobin ratios estimated. Cycled animals were distinct from those at constant temperatures in several respects. Hematological parameters were elevated above those of animals at constant temperature and were, on a diurnal basis, more stable. Red blood cell electrolyte levels varied in an adaptively appropriate fashion to cycle temperatures. This was not the case in the constant temperature groups_ Under the cycling regime, plasma ion levels were more diurnally stable than those of constant temperature fish. Although muscle parameters in cycled fish exhibited more fluctuation than was observed in plasma, these also tended to be relatively more stable than was the caseErythrocytic data are discussed in terms of their effects on hemoglobin-oxygen affinity while plasma and muscle observations were considered from the standpoint of overall water-electrolyte balance. In general, cycled fish appeared to be capable of stabilizing overall body fluid composition, while simultaneously effecting adaptively-appropriate modifications in the erythrocytic ionic microenvironment of hemoglobin. The sometimes marked diurnal variability of water-electrolyte status in animals held at constant temperature as opposed to the conservation of cycled fish suggests that this species is, in some fashion, programmed for regulation in a thermally-fluctuating environment. If this interpretation is valid and a phenomenon of general occurrence, some earlier studies involving constant acclimation of eurythermal species normally occupying habitats which vary in temperature on a daily basis may require reconsideration. at constant temperature.

NMR studies of mixed tetrahaloborates and some related boron trihalide complexes /|nGary John Schrobilgen. -- 260 St. Catharines, Ont. : [s. n.],

Nuclear magnetic resonance spectroscopy has been used to study donor-acceptor complexes of boron trifluoride with several ureas, tetramethylthiourea, tetramethylselenourea, and tetramethylquanidine as well as adducts of tetramethyl- -urea with BF2Cl, BFC1 2 , and BC1 3 - A large number of mixed tetrahaloborate ions, including some of the ternary ones such as BF2CIBr-,have been obtained by ligand exchange reactions and studied by NMR techniques. The bonding in these ions is of the same inherent interest as the bonding in the isoelectronic tetrahalomethanes which have been the subject of many detailed studies and have been involved in a controversy concerning the existence of and the nature of "fluorine hyperconjugation" or C-F P1T- Pn bonding_ Ligand exchange reactions also gave rise to the difluoroboron cation, (TMU)20BF2+o The difluoroboron cation has been observed in solutions of TMU-BF3 , and has been proposed as a possible intermediate for fluorine exchange reactions in BF3 adducts.

Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.

Studies of some cocondensations of nickel atoms with unsaturated organic ligands and with mixed ligand systems

The cocondensation of nickel with a number of unsaturated ligands was studied, as was the cocondensation with a number of mixed ligand systems. Enamines were found not to react with nickel while acrylonitrile was polymerized. In the mixed ligand syst.ems different products were obtained than when the ligands were cocondensed individually. Cocondensations of benzyl halide/allyl halide mixtures gave unstable products that were not observed when the halides were cocondensed individually. The effect of Kao-Wool insulation on nickel/benzyl halide cocondensations was found to be significant. Kao-Wool caused the bulk of the benzyl halide to be polymeri zed to a number of poly-benzylic species. An alkali metal reactor was designed for the evaporation of sodium and potassium atoms into cold solutions of metal halide and an or ganic substrate. This apparatus was used to synthesize Ni(P¢3 )3' but proved unsuccessful for synthesizing a nickel-enamine compound.

Phospha-adamantane ligands and phosphorous ionic liquids for palladium-catalyzed cross-coupling reactions /

New and robust methodologies have been designed for palladiumcatalyzed cross-coupling reactions involving a library of novel tertiary phosphine ligands incorporating a phospha-adamantane framework. The secondary phosphine, l,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane was converted into a small library of tertiary phosphine derivatives and the ability of these tertiary phosphaadamantanes to act as effective ligands in the palladium-catalyzed amination reaction and p-alkyl-Suzuki cross-coupling was examined. l,3,5,7-Tetramethyl-6- phenyl-2,4,8-trioxa-6-phosphaadamantane (PA-Ph) used in combination with Pd2(dba)3 CHCI3 facilitated the reaction of an array of aryl iodides, bromides and chlorides with a variety secondary and primary amines to give tertiary and secondary amines respectively in good to excellent yields. 8-(2,4-Dimethoxyphenyl)- l,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-tricyclo[3.3.1.1*3,7*]decane used in combination with Pd(0Ac)2 permitted the reaction of an array of alkyl iodides, and bromides with a variety aryl boronic acids and alkyl 9-BBN compounds in good to excellent yields. Subsequent to this work, the use of phosphorous based ionic liquids, specifically tetradecyltrihexylphosphonium chloride (THPC), in the Heck reaction provided good to excellent yields in the coupling of aryl iodides and bromides with a variety of olefins.

The mechanism of formation of the mixed boron trihalide adducts of trimenthylamine

Boron trihalide and mixed boron trihalide adducts of trimethylamine have been prepared, and characterized by proton and fluorine N.M.R. spectroscopy. The acceptor power of the boron trihalides was seen to increase in the order BF3 < BC13 < BBr3 < BI3, corroborating previous evidence. The mixed boron trihalides had intermediate Lewis acidities. Solution reactions between adducts and free boron trihalides rapidly led to the formation of mixed adducts when the free boron trihalide is a stronger Lewis acid than that in the adduct. A slower reaction is observed when the free BX3 is a weaker Lewis aoid than that complexed. The mechanism of halogen exchange leading to the mixed (CH3)3NBX3 adducts was investigated. 10B labelling experiments precluded B-N bond rupture as a possible mechanism in solution; results are discussed in terms of halogen-bridged intermediates. Pre-ionization may be important for some systems. At higher temperatures, during gas phase reactions,B-N coordinate bond rupture may be the initial step of reaction. Two mixed adduots, namely (CH3)3NBClBr2 and (CH3)3NBHOIBr were prepared and characterized by Mass Spectrometry

Spin labile conducting metallopolymers : a new architecture for hybrid multifunctional materials

The synthesis of 3-ethynylthienyl- (2.07), 3-ethynylterthienyl- (2.19) substituted qsal [qsalH = N-(8-quinolyl)salicylaldimine] and 3,3' -diethynyl-2,2' -bithienyl bridging bisqsal (5.06) ligands are described along with the preparation and characterization of eight cationic iron(III) complexes containing these ligands with a selection of counteranions [(2.07) with: SCN- (2.08), PF6- (2.09), and CI04- (2.10); (2.19) with PF6 - (2.20); (5.06) with: cr (5.07), SeN- (5.08), PF6- (5.09), and CI04- (5.10)]. Spin-crossover is observed in the solid state for (2.08) - (2.10) and (5.07) - (5.10), including a ve ry rare S = 5/2 to 3/2 spin-crossover in complex (2.09). The unusal reduction of complex (2.10) produces a high-spin iron(I1) complex (2.12). Six iron(II) complexes that are derived from thienyl analogues of bispicen [bispicen = bis(2-pyridylmethyl)-diamine] [2,5-thienyl substituents = H- (3.11), Phenyl- (3.12), 2- thienyl (3.13) or N-phenyl-2-pyridinalimine ligands [2,5-phenyl substituents = diphenyl (3.23), di(2-thienyl) (3.24), 4-phenyl substituent = 3-thienyl (3.25)] are reported Complexes (3.11), (3.23) and (3.25) display thermal spin-crossover in the solid state and (3.12) remains high-spin at all temperatures. Complex (3.13) rearranges to form an iron(II) complex (3.14) with temperature dependent magnetic properties be s t described as a one-dimensional ferromagnetic chain, with interchain antiferromagnetic interactions and/or ZFS dominant at low temperatures. Magnetic succeptibility and Mossbauer data for complex (3.24) display a temperature dependent mixture of spin isomers. The preparation and characterization of two cobalt(II) complexes containing 3- ethynylthienyl- (4.04) and 3-ethynylterhienyl- (4.06) substituted bipyridine ligands [(4.05): [Co(dbsqh(4.04)]; (4.07): [Co(dbsq)2(4.06)]] [dbsq = 3,5-dbsq=3,5-di-tert-butylI ,2-semiquinonate] are reported. Complexes (4.05) and (4.07) exhibit thermal valence tautomerism in the solid state and in solution. Self assembly of complex (2.10) into polymeric spheres (6.11) afforded the first spincrossover, polydisperse, micro- to nanoscale material of its kind. . Complexes (2.20), (3.24) and (4.07) also form polymers through electrochemical synthesis to produce hybrid metaUopolymer films (6.12), (6.15) and (6.16), respectively. The films have been characterized by EDX, FT-IR and UV-Vis spectroscopy. Variable-temperature magnetic susceptibility measurements demonstrate that spin lability is operative in the polymers and conductivity measurements confirm the electron transport properties. Polymer (6.15) has a persistent oxidized state that shows a significant decrease in electrical resistance.