Thesis advisor: Michael J. Naughton / Quasi-one dimensional (Q1D) molecular organic conductors are among the most exciting materials in condensed matter physics, exhibiting nearly every known ground state. They are highly anisotropic, structurally and electronically, and show large oscillatory phenomena in conductivity for magnetic field rotated in different crystalline planes. Several theoretical works have been published to explain these angular magnetoresistance oscillation (AMRO) effects, but the underlying physics remains illunderstood. Here, we present measurements and calculations of magnetotransport in the molecular organic (super)conductor (DMET)₂I₃ which detect and simulate all known AMRO phenomena for Q1D systems. Employing, for the first time, the true triclinic crystal structure in the calculations, these results address the mystery of the putative vanishing of the primary AMRO phenomenon, the Lebed magic angle effect, for orientations in which it is expected to be strongest. They also show a common origin for Lebed and so-called "Lee-Naughton" oscillations, and confirm the generalized nature of AMRO in Q1D systems. Furthermore, we report the temperature dependence of the upper critical magnetic field in (DMET)₂I₃, for magnetic field applied along the intrachain, interchain, and interplane directions. The upper critical field exhibits orbital saturation at low temperature for field in all directions, implying that superconductivity in (DMET)₂I₃ is conventional spin singlet. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22685号 / 理博第4626号 / 新制||理||1665(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 前里 光彦, 教授 吉村 一良, 教授 有賀 哲也 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

This thesis deals with the synthesis of electroactiveorganic compounds. The synthesis of ethylenedioxy-benzodioxinstri-dioxin and tetra-dioxin are described. These molecules wereprepared with the aim of creating donor molecules for cationicradical salts. The symmetric analogs of tri-dioxin,methylenedioxy-derivative and ethylenedioxy-naphthalene werealso synthesized. Three different cation radical salts with 2:1stoichiometries were obtained from tri-dioxin, whiletetra-dioxin merely provided polycrystalline materials.Tri-dioxin and tetra-dioxin were also successful as operationalmatrixes in PALDI-TOF. Tetrathiafulvalenes with the2-dialkyl-amino-1,3-dithiolium-4-thiolate mesoion asbuilding-block was also synthesized. A series of doublyalkylthiol-substituted TTFs were prepared with the aim offorming self-assembly monolayers on gold surfaces in theapplication of organic thin film field-effect transistors.Film-formation for two TTFs were studied and they providedrelatively dense packed monolayers with a discrete distance ofthe TTF moiety from the gold surface. The mesoionic compound was also for the first time used inanumpolungreaction. The electrophile obtained in situ bytreatment of mesoion with sulfuryl chloride was reacted with avariety of electron-rich aromatic compounds. From the receivedproducts three new arylthio-substituted TTFs weresynthesized. <b>Keywords:</b>Synthesis, Benzodioxin, Tetrathiafulvalene,Mesoion, Organic Conductor, Cation Radical Salt, CyclicVoltammetry, Electrocrystallization, Self-Assembly Monolayer,SAM, Organic Field-Effect Transistor, OFET

<p>This thesis deals with the synthesis of electroactiveorganic compounds. The synthesis of ethylenedioxy-benzodioxinstri-dioxin and tetra-dioxin are described. These molecules wereprepared with the aim of creating donor molecules for cationicradical salts. The symmetric analogs of tri-dioxin,methylenedioxy-derivative and ethylenedioxy-naphthalene werealso synthesized. Three different cation radical salts with 2:1stoichiometries were obtained from tri-dioxin, whiletetra-dioxin merely provided polycrystalline materials.Tri-dioxin and tetra-dioxin were also successful as operationalmatrixes in PALDI-TOF.</p><p>Tetrathiafulvalenes with the2-dialkyl-amino-1,3-dithiolium-4-thiolate mesoion asbuilding-block was also synthesized. A series of doublyalkylthiol-substituted TTFs were prepared with the aim offorming self-assembly monolayers on gold surfaces in theapplication of organic thin film field-effect transistors.Film-formation for two TTFs were studied and they providedrelatively dense packed monolayers with a discrete distance ofthe TTF moiety from the gold surface.</p><p>The mesoionic compound was also for the first time used inan<i>umpolung</i>reaction. The electrophile obtained in situ bytreatment of mesoion with sulfuryl chloride was reacted with avariety of electron-rich aromatic compounds. From the receivedproducts three new arylthio-substituted TTFs weresynthesized.</p><p><b>Keywords:</b>Synthesis, Benzodioxin, Tetrathiafulvalene,Mesoion, Organic Conductor, Cation Radical Salt, CyclicVoltammetry, Electrocrystallization, Self-Assembly Monolayer,SAM, Organic Field-Effect Transistor, OFET</p>