Over the past twenty years molecules capable of templating their own synthesis, so called self–replicating molecules have gained prominence in the literature. We show herein that mixing the reagents for replicating molecules can produce a network of self–replicators which coexist and that the networks can be instructed by the addition of preformed template upon initiation of the reaction. Whilst self–replicating molecules offer the simplest form of replication, nature has evolved to utilise not minimal self–replication but reciprocal replication where one strand templates the formation of not an identical copy of itself but a reciprocal strand. Efforts thus far at producing a synthetic reciprocal replicating system are discussed and an alternative strategy to address the problems encountered is proposed and successfully implemented. The kinetic behaviour of a self–replicating reaction bears two distinctive time periods. Upon initiation, the reaction proceeds slowly as no template exists to catalyse the reaction. Upon production of the template, the reaction proceeds more rapidly via template direction. During this slow reaction period, the system is prone to mistakes as the reaction is slow and unselective. The creation of an [A•B] binary complex through non–covalent recognition of reagents allows for the reaction to proceed at an accelerated rate upon initiation however products of such a reaction are usually catalytically inert and do not promote further template directed reaction. A strategy to combine the desired behaviour of an [A•B] binary complex with the further template directed autocatalytic self–replicating reaction is described and implemented. Supramolecular polymers consist of repeating monomers which are held together by non–covalent interactions. The strong association of a self–replicating template dimer is comparable to that of supramolecular polymers reported thus far in the literature which are produced by cumbersome standard linear synthetic procedures. Herein the application of self–replication to the field of supramolecular polymer synthesis is discussed. As the autocatalytic reaction to produce the template monomers occurs under the same conditions as required to allow polymerisation to proceed, the polymer is able to spontaneously form in situ by self–replicating supramolecular polymerisation.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

No description available.

This thesis presents the synthesis and characterisation of a range of heterometallated porphyrin oligomers and other novel 3D π-conjugated porphyrin nanostructures. Subsequently, their physical organic properties were evaluated which revealed some fascinating electronic properties. Chapter 1 summarises some of the work done in the Anderson group on porphyrin nanostructures and reviews the literature regarding heterometallated porphyrin oligomers. In addition it introduces the main concepts and techniques used in the remainder of the thesis. In Chapter 2 the stabilities of a family of four linear porphyrin pentamer complexes are determined by UV-vis-NIR titrations and analysed using chemical double-mutant cycles which reveal that the binding energy of the copper centre to an axial pyridine ligand is -6.2 kJ mol^-1. Subsequently, the Zn-Zn-Cu-Zn-Zn pentamer is used in the synthesis of a heterometallated 10-porphyrin nanoring. Chapter 3 will describe the investigation of quantum interference phenomena in a bis-copper six-porphyrin nanoring by using EPR spectroscopy. We show that the exchange coupling between two spin centres is increased by a factor 4.5 in the ring structure with two parallel coupling pathways as compared to an otherwise identical system with just one coupling path. In Chapter 4 the syntheses of three isomers of the bis-copper 6-porphyrin nanoring are described. DFT calculations have indicated potential destructive interference phenomena in one of the isomers which would allow for the formation of a molecular system with behaviour resembling that of a hypothetical molecular interferometer. Chapter 5 reports on the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This bicyclic structure consists of two intersecting nanorings of 6 and 10 porphyrin units. Fluorescence up-conversion spectroscopy experiments demonstrate that electronic excitation delocalises over the whole 3D π-system within 0.3 ps if the nanoball is bound to its templates or within 5 ps if the nanoball is empty. In Chapter 6 the synthesis and characterisation of a D_4h symmetric analogue of the porphyrin nanoball is described. The structure consists of ten porphyrin units arranged as two perpendicular 6-porphyrin nanorings intersecting at two porphyrins. In the synthesis, a combination of magnesium and zinc porphyrins are used which allows for the introduction of a selective demetallation method crucial for accessing this novel structure.

Currently, there is interest in the development of molecular-scale devices for use in quantum information processing (QIP). With this application in mind, physical studies on antiferromagnetically coupled molecular wheels [Cr7MF3(Etglu)(O2CtBu)15(phpy)], where M is a divalent metal cation (M = Mn2+, Zn2+, Ni2+) have been pursued. The heterometallic wheels contain an octagon of metal centres, which are bridged by fluoride ions, pivalate groups and a chiral N-ethyl-D-glutamine molecule which is penta-deprotonated and bound to the metal sites through all available O-donors. They are deep purple in colour and they have been named purple-Cr7M. There is antiferromagnetic coupling between adjacent metal centres, J » -8 cm-1, resulting in a non-zero net spin ground state. The spin-Hamiltonian parameters of this family have been determined.At the heterometal site of purple-Cr7M wheels there is a terminal ligand which can be substituted for a variety of N-donor organic ligands. A series of bidentate N-donor linkers has been used to link Cr7Ni wheels (each wheel Seff = 1/2) to create prototype two-qubit systems. Multi-frequency EPR spectroscopy and SQUID magnetometry has been used to extract the spin-Hamiltonian parameters of this family. It has been shown that the single wheels can be linked together electronically as well as chemically. It has been found that for the unsaturated linkers, there is a weaker interaction between Cr7Ni wheels when longer linkers are used. The strength of interaction is smaller for the saturated linkers than for the unsaturated linkers.The formation of 'green'-Cr7M wheels is different, being templated around a cation. Two new types of wheels have been studied: [tBuCONHC6H12NH2C6H12NHCOtBu][Cr7M2+F8(O2CtBu)16] and [Cs?Cr7MF8(O2CtBu)16]·0.5MeCN (where, M = Mn2+, Zn2+, Ni2+), where the former is templated around a long dialkylammonium group and the latter around a caesium cation. The effect of the templating cation on spectroscopic properties has been determined.Physical studies on a family of antiferromagnetically-coupled homometallic clusters have been pursued. They consist of cyclic arrays of homometallic Cr3+ ions in either a octametallic wheel or hexametallic horseshoes. The horseshoes have the general formula: [CrxFx+5L2x-2]n3- (where L = carboxylate). Cr3+ centres are bridged by pivalate groups and fluorides, while Cr3+ centres at the ends of the chain have terminal fluorides completing their coordination sphere. These terminal fluoride groups are labile enough to be substituted, e.g. [EtNH2][Cr6F7(O2CtBu)10(acac)2] is the product of a substitution reaction with acetylacetone.

This thesis investigates the design and synthesis of macrocycles and examines their ion-pair recognition, anion recognition and interpenetrative assembly capabilities. Chapter One introduces the field of supramolecular chemistry. Key concepts in host–guest complexation and self-assembly are outlined, with particular emphasis on the design of host systems for anion and ion-pair recognition. Chapter Two details the synthesis and binding properties of a heteroditopic 1,2,3-triazole- containing macrocycle that exhibits cooperative ion-pair recognition. Solution and solid-state evidence shows that the triazole motif simultaneously binds anions and cations. The exten- sion of this work towards the formation of interlocked structures containing an expanded heteroditopic macrocycle and threading components is explored. Chapter Three discusses the design and syntheses of series of electron-deficient macrocycles based on imidazolium, pyridinium and triazole. These are investigated for anion binding ability and assembly of interpenetrative assemblies with electron-rich threading components. Chapter Four describes research into the formation of interpenetrative assemblies using neutral components. Their design is based around aromatic donor–acceptor interactions and halogen bonding. Chapter Five presents some conclusions from the research undertaken. Chapter Six provides titration protocols, Job plot approximations, experimental procedures and characterisation of the compounds described in this thesis. Appendix details additional X-ray crystallographic data.

This thesis explores the use of anions in the design and construction of interlocked architectures for applications in anion recognition and sensing, and to function as molecular machines upon a given stimulus. Chapter One introduces the field of anionic supramolecular chemistry focusing on host-guest chemistry and directed self-assembly. A review of the recognition and sensing of anionic guest species is given before strategies for the construction of interlocked architectures are discussed, and the potential functions of these structures considered. Chapter Two details the development of a novel anion-templation route for the synthesis of macrocycles and rotaxanes. The versatility of this route in constructing new [2]rotaxanes is explored by varying several features of the macrocyclic component, with emphasis on creating the most powerful anion complexant. Proton NMR spectroscopy is used to probe the anion binding properties of the rotaxanes, and X-ray crystallography and MD simulations are used to rationalize anion binding trends. The possibility of synthesizing catenanes for anion recognition via this new synthetic route is also investigated. Chapter Three investigates the appendage of transition metal complexes to rotaxanes to create interlocked host architectures capable of sensing anions via luminescence spectroscopy. The incorporation of rhenium(I) and ruthenium(II) polypyridyl complexes into the macrocyclic and axle component of [2]rotaxanes are described, before the anion binding studies of these structures using ¹H NMR and luminescence spectroscopy are reported. Chapter Four describes the strategic synthesis of [2]rotaxanes designed to undergo molecular motion upon a given stimulus. Initially, the possibility of exploiting anions to stimulate the macrocyclic component of the [2]rotaxanes to translocate to a second station on the axle is investigated. The use of pyridine N-oxide as an integrated template for rotaxane formation is reported before the ability of these rotaxanes to undergo anion and pH driven molecular motion is explored. This chapter concludes with the construction of a calix[4]diquinone N-oxide containing [2]rotaxane capable of undergoing sodium- and barium-induced molecular pirouetting. Chapter Five provides synthetic procedures and characterisation details for compounds listed in this thesis. Chapter Six reports supplementary experimental information including titration protocols, X-ray crystal structures and MD simulations.

Neste trabalho são descritas as propriedades morfológicas, condutoras, fotoeletroquímicas e eletrocatalíticas de filmes de porfirinas supramoleculares, contendo complexos de rutênio polipiridina e clusters trinucleares de rutênio. Foram empregadas técnicas de microscopia de varredura por sonda, voltametria cíclica, espectroscopia de impedância eletroquímica, espectroeletroquímica UV-vis, voltametria de disco rotatório e experimentos combinados de eletroquímica/fotoeletroquímica. Cálculos semi-empíricos foram utilizados em alguns casos para dar maior suporte às interpretações. O método de preparação dos filmes tem efeito drástico sobre o tipo de empacotamento do material. Conseqüentemente, as propriedades condutoras e fotoeletroquímicas também são afetadas. Por exemplo, o coeficiente de difusão eletrônica (DeCm2) pode variar até 104 vezes dependendo do tipo de empacotamento de uma mesma porfirina utilizada. Os processos de condução desses filmes são controlados por um mecanismo redox envolvendo os sítios de rutênio e são mediados por orbitais &#906;* dos anéis porfirínicos e polipiridínicos. A intensidade de fotocorrente em função do &#955; incidente depende do mecanismo de transporte de elétrons e pode ser modulada pela natureza e grau de acoplamento eletrônico entre os anéis porfirínicos dentro do filme. Esses filmes exibem propriedades eletrocatalíticas na oxidação de substratos de interesse ambiental, da indústria alimentícia e do setor médico, tais como nitrito, sulfito e ácido ascórbico. As eficiências desses materiais são altas, com kf > 104 mol-1dm3s-1. Em catalisadores redox foi verificada uma tendência exponencial entre a constante cinética de transferência eletrônica heterogênea e potencial de E1/2 do centro redox no filme, como previsto pela equação de Marcus. A cobalto porfirina contendo quatro clusters trinucleares de rutênio se comporta como um eficiente catalisador molecular da redução do O2 por 4 elétrons, em pH < 5. O mecanismo de redução não envolve a bis-coordenação do O2 a dois sítios metálicos. Nesse caso, efeitos eletrônicos dos complexos periféricos devem ativar o centro da metaloporfirina, promovendo a transferência multieletrônica e prevenindo a formação de espécies reativas, como OH· e O2-. Uma célula de FIA foi construída visando a análise quantitativa de sulfito, exibindo alta eficiência em termos de limite de detecção, freqüência de análises e reprodutibilidade. O sistema FIA foi adaptado e empregado juntamente com o filme de uma porfirina supramolecular para reproduzir as funções básicas de um portal lógico, exibindo comportamento singular, podendo desempenhar as três funções (AND, OR e NOT) num único sistema químico integrado. / A full characterization of the morphologic, conduction, photoelectrochemical and electrocatalytic properties of supramolecular porphyrin films containing ruthenium polypyridyl or ruthenium clusters, is described. Techniques, such as scanning probe microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, UV-vis spectroelectrochemistry, rotating disk electrode voltammetry, and combined electrochemical/photoelectrochemical experiments were employed. Semi-empirical calculations were utilized in order to obtain more information on the interpretations. The preparation method of film deposition has a special effect on the material packing. Consequently, the conduction and photoelectrochemical properties are also affected. For example, the electronic diffusion coefficient (DeCm2) differs by up to 104 times depending on the packing characteristics of the same porphyrin material. The conduction process is limited by a redox mechanism involving the ruthenium centers and is mediated by &#960;* orbitals of the porphyrin or polypyridine species. The photocurrent intensity as a function of the incident &#955; depends on the electron transport mechanism involved and this can be tuned by the nature and the degree of electronic coupling between the porphyrin rings, in the film. This kind of films also exhibits electrocatalytic activities for the oxidation of substrates with interests in the environmental, food and medical areas, such as nitrite, sulfite, and ascorbic acid. The efficiency of these materials are also high, with kf > 104 mol-1dm3s-1. An exponential relationship of the heterogeneous electron transfer kinetic constant with the E1/2 of the redox center was found, as predicted by the Marcus equation. The cobalt porphyrin containing four ruthenium clusters behaves as an efficient catalyst for the 4-electron reduction of O2, at pH <5. The mechanism does not involve the bis-coordination of O2 to two metallic centers, but electronic effects from the ruthenium clusters should be activating the metalloporphyrin center, promoting the multi-electronic transfer and preventing the formation of reactive species, such as OH· e O2-. A FIA cell was built in order to provide a quantitative analysis of sulfite, and it exhibited high sampling frequency, reproducibility, as confirmed by the low detection limit (0.1 &#181;mol.dm-3). The FIA system was adapted and employed with a supramolecular porphyrin film as logic gates and they exhibited a unique behavior, operating the three basic functions (AND, OR and NOT) in a single integrated chemical system.

Neste trabalho são descritas as propriedades morfológicas, condutoras, fotoeletroquímicas e eletrocatalíticas de filmes de porfirinas supramoleculares, contendo complexos de rutênio polipiridina e clusters trinucleares de rutênio. Foram empregadas técnicas de microscopia de varredura por sonda, voltametria cíclica, espectroscopia de impedância eletroquímica, espectroeletroquímica UV-vis, voltametria de disco rotatório e experimentos combinados de eletroquímica/fotoeletroquímica. Cálculos semi-empíricos foram utilizados em alguns casos para dar maior suporte às interpretações. O método de preparação dos filmes tem efeito drástico sobre o tipo de empacotamento do material. Conseqüentemente, as propriedades condutoras e fotoeletroquímicas também são afetadas. Por exemplo, o coeficiente de difusão eletrônica (DeCm2) pode variar até 104 vezes dependendo do tipo de empacotamento de uma mesma porfirina utilizada. Os processos de condução desses filmes são controlados por um mecanismo redox envolvendo os sítios de rutênio e são mediados por orbitais &#906;* dos anéis porfirínicos e polipiridínicos. A intensidade de fotocorrente em função do &#955; incidente depende do mecanismo de transporte de elétrons e pode ser modulada pela natureza e grau de acoplamento eletrônico entre os anéis porfirínicos dentro do filme. Esses filmes exibem propriedades eletrocatalíticas na oxidação de substratos de interesse ambiental, da indústria alimentícia e do setor médico, tais como nitrito, sulfito e ácido ascórbico. As eficiências desses materiais são altas, com kf > 104 mol-1dm3s-1. Em catalisadores redox foi verificada uma tendência exponencial entre a constante cinética de transferência eletrônica heterogênea e potencial de E1/2 do centro redox no filme, como previsto pela equação de Marcus. A cobalto porfirina contendo quatro clusters trinucleares de rutênio se comporta como um eficiente catalisador molecular da redução do O2 por 4 elétrons, em pH < 5. O mecanismo de redução não envolve a bis-coordenação do O2 a dois sítios metálicos. Nesse caso, efeitos eletrônicos dos complexos periféricos devem ativar o centro da metaloporfirina, promovendo a transferência multieletrônica e prevenindo a formação de espécies reativas, como OH· e O2-. Uma célula de FIA foi construída visando a análise quantitativa de sulfito, exibindo alta eficiência em termos de limite de detecção, freqüência de análises e reprodutibilidade. O sistema FIA foi adaptado e empregado juntamente com o filme de uma porfirina supramolecular para reproduzir as funções básicas de um portal lógico, exibindo comportamento singular, podendo desempenhar as três funções (AND, OR e NOT) num único sistema químico integrado. / A full characterization of the morphologic, conduction, photoelectrochemical and electrocatalytic properties of supramolecular porphyrin films containing ruthenium polypyridyl or ruthenium clusters, is described. Techniques, such as scanning probe microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, UV-vis spectroelectrochemistry, rotating disk electrode voltammetry, and combined electrochemical/photoelectrochemical experiments were employed. Semi-empirical calculations were utilized in order to obtain more information on the interpretations. The preparation method of film deposition has a special effect on the material packing. Consequently, the conduction and photoelectrochemical properties are also affected. For example, the electronic diffusion coefficient (DeCm2) differs by up to 104 times depending on the packing characteristics of the same porphyrin material. The conduction process is limited by a redox mechanism involving the ruthenium centers and is mediated by &#960;* orbitals of the porphyrin or polypyridine species. The photocurrent intensity as a function of the incident &#955; depends on the electron transport mechanism involved and this can be tuned by the nature and the degree of electronic coupling between the porphyrin rings, in the film. This kind of films also exhibits electrocatalytic activities for the oxidation of substrates with interests in the environmental, food and medical areas, such as nitrite, sulfite, and ascorbic acid. The efficiency of these materials are also high, with kf > 104 mol-1dm3s-1. An exponential relationship of the heterogeneous electron transfer kinetic constant with the E1/2 of the redox center was found, as predicted by the Marcus equation. The cobalt porphyrin containing four ruthenium clusters behaves as an efficient catalyst for the 4-electron reduction of O2, at pH <5. The mechanism does not involve the bis-coordination of O2 to two metallic centers, but electronic effects from the ruthenium clusters should be activating the metalloporphyrin center, promoting the multi-electronic transfer and preventing the formation of reactive species, such as OH· e O2-. A FIA cell was built in order to provide a quantitative analysis of sulfite, and it exhibited high sampling frequency, reproducibility, as confirmed by the low detection limit (0.1 &#181;mol.dm-3). The FIA system was adapted and employed with a supramolecular porphyrin film as logic gates and they exhibited a unique behavior, operating the three basic functions (AND, OR and NOT) in a single integrated chemical system.