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ABSTRACT Electricity is vital for modern life. With the rapid development of industries, society, and the ever-increasing population worldwide, the demand for electricity and advanced modern electronic devices with multifunctionality has increased tremendously. Therefore, advanced electronic materials that meet the requirements of the modern electronics and energy industry are needed. Electrically conductive metal-organic frameworks (EC-MOFs), composed of metal clusters acting as nodes and organic ligands as linkers connected by coordination bonds, are among the most promising materials due to their tunable structures, properties, and diverse functions. However, the lack of comprehensive understanding of their structure-property relationship hinders the development of EC-MOFs. My dissertation focuses on the design, construction, and structure-property relationship studies of EC-MOFs. Chapter 1 describes how MOFs' structural features and compositions affect the electronic properties and demonstrates conductive mechanisms and the corresponding design strategies to develop EC-MOFs. Chapter 2 describes the synthesis, characterization, electronic and optical properties, and structure-property relationships of four novel alkali metal (Na, K, Rb, and Cs) and an electron-rich tetrathiafulvalene tetracarboxylate (TTFTC) ligand-based 3D-MOFs where the ligands form continuous π-stacks and become partially oxidized by air forming TTFTC•+ radical cations. Depending on the π–π distance and TTFTC•+ population, the MOFs enjoyed different degrees of intervalence charge transfer (IVCT) interaction, which commensurately affected their band gaps and electrical conductivity. Chapter 3 depicts a novel design strategy to enhance the bulk electrical conductivity of 2D graphitic MOFs by promoting simultaneous in-plane and out-of-plane charge transport. To this end, we have synthesized the first π-intercalated two-dimensional graphitic MOF (iGMOF1) through an elegant bottom-up synthesis method. This novel structure featured hexagonal Cu-HATP (hexaaminotriphenylene, HATP) coordination network and built-in alternating π-donor/acceptor stacks of electron-rich HATP ligands and non-coordinatively intercalated π-acceptors hexacyano-triphenylene (HCTP) molecules, which simultaneously facilitated both in-plane and out-of-plane to endow iGMOF1 with higher bulk electrical conductivity compared to pristine Cu3(HATP)2. Chapter 4 describes design, synthesis, and structure-property relationship studies of a novel 2D Cu3(HOTP)(HHTQ) MOF based on a π-donor 2,3,6,7,10,11-hexahydrotriphenylene (HOTP) ligand and a π-acceptor 2,3,7,8,12,13-Hexahydroxytricycloquinazoline (HHTQ) ligand. The resulting framework featured continuous out-of-plane π-D/A stacks and in-plane hexagonal π-D-A sheets, promoting through-space and through-bond charge transport, respectively, which gave rise to a bulk electrical conductivity than pristine Cu3(HOTP)2 and Cu3(HHTQ)2. Finally, Chapter 5 describes the transformation of a collapse-prone, electrically insulating MOF-74 analog into structurally more stable, porous, and electrically conductive MOF/PEDOT composites. 

For simultaneous testing of multivariate normal means with known correlation matrix against two-sided alternatives, this paper introduces new methods with proven finite-sample control of false discovery rate. The methods are obtained by shifting each p-value to the left and considering a Benjamini–Hochberg-type linear step-up procedure based on these shifted p-values. The amount of shift for each -value is appropriately determined from the correlation matrix to achieve the desired false discovery rate control. Simulation studies and real-data application show favorable performances of the proposed methods when compared with relevant competitors. 

Due to their diverse potential in advanced electronics and energy technologies, electrically conducting metal–organic frameworks (MOFs) are drawing significant attention. Although hexagonal 2D MOFs generally display impressive electrical conductivity because of their dual in-plane (through bonds) and out-of-plane (through π-stacked ligands) charge transport pathways, notable differences between these two orthogonal conduction routes cause anisotropic conductivity and lower bulk conductivity. To address this issue, we have developed the first redox-complementary dual-ligand 2D MOF Cu3(HHTP)(HHTQ), featuring a π-donor hexahydroxytriphenylene (HHTP) ligand and a π-acceptor hexahydroxytricycloquinazoline (HHTQ) ligand located at alternate corners of the hexagons, which form either parallel HHTP and HHTQ stacks (AA stacking) or alternating HHTP/HHTQ stacks (AB stacking) along the c-axis. Regardless of the stacking pattern, Cu3(HHTP)(HHTQ) supports more effective out-of-plane conduction through either separate π-donor and π-acceptor stacks or alternating π-donor/acceptor stacks, while promoting in-plane conduction through the push–pull-like heteroleptic coordination network. As a result, Cu3(HHTP)(HHTQ) exhibits higher bulk conductivity (0.12 S/m at 295 K) than single-ligand MOFs Cu3(HHTP)2 (7.3 × 10–2 S/m) and Cu3(HHTQ)2 (5.9 × 10–4 S/m). This work introduces a new design approach to improve the bulk electrical conductivity of 2D MOFs by supporting charge transport in both in- and out-of-plane directions. 

Abstract We report copper(II) and copper(III) trifluoromethyl complexes supported by a pyridinedicarboxamide ligand (L) as a platform for investigating the role of electron transfer in C(sp²)−H trifluoromethylation. While the copper(II) trifluoromethyl complex is unreactive towards (hetero)arenes, the formal copper(III) trifluoromethyl complex performs C(sp²)−H trifluoromethylation of a wide range of (hetero)arenes. Mechanistic studies using the copper(III) trifluoromethyl complex suggest that the mechanism of arene trifluoromethylation is substrate‐dependent. When the thermodynamic driving force for electron transfer is high, the reaction proceeds through a previously unidentified single electron transfer (SET) mechanism, where an initial electron transfer occurs between the substrate and oxidant prior to CF₃group transfer. Otherwise, a CF₃radical release/electrophilic aromatic substitution (S_EAr) mechanism is followed. These studies provide valuable insights into the role of strong oxidants and potential mechanistic dichotomy in Cu‐mediated C(sp²)−H trifluoromethylation.