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The use of two different chelating redox active ligands, 2,6-bis(6-methyl-1,2,4,5-3-yl) pyridine (BTZP) and 2,6-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridine (BTP) in heterometallic first row and second row transition metal chemistry has yielded two new families of redox active metal complexes. These complexes were found to exhibit interesting electrochemical and magnetic properties. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of the ligand design, ligand synthesis and related coordination chemistry literature review. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of discrete molecules and supramolecular arrangements, employing the ligand BTZP, is presented. All of the complexes presented in Chapter 2 are successfully synthesized and characterized with electrochemical and magnetic studies. According to the electrochemical data, it is found that the classic “terpy-like” complexes with [Co(BTZP) 2]2+ formula fosters more stability in the redox process. In Chapter 3, a family of transition metal complexes with [M(BTP) 2]2+ (M=Fe or Co) inorganic cores were obtained through the employment of the ligand BTP with various anions. In addition, dimeric molecules with [CoX4(BTP)2] formula were also obtained by solvothermal synthesis. The complexes were also electrochemically characterized, with all the complexes capable of being reduced, while only [CoII(BTP)2] (ClO4)2 showed reversible redox process. Similar with BTZP, the series of BTP based complexes are also characterized through magnetic measurement. Only cobalt-based BTP complexes are paramagnetic, with [CoII(BTP)2]2+ being spin crossover active when BF4- and ClO4- are present. However, the presence of NCS- and halides lead to either antiferromagnetic interactions and ferromagnetic interactions dominating at different temperature regimes.

N-methyl-6-hydroxyquinolinium (NM6HQ) is a powerful excited-state proton donor, exhibiting a huge pKa drop from 7.2 in the ground state to -7 in the excited state. The zwitterionic nature of the proton transfer product encourages intramolecular electron transfer away from the hydroxyl moiety to the distal ring, allowing for a large pKa jump in the excited state. This process is reversible, making the NM6HQ salts powerful transient superacids. We have investigated the excited-state proton transfer (ESPT) from NM6HQ salts to various basic solvents (alcohols, DMSO). A model has been developed that adequately describes the ion-dipole interactions in the ESPT geminate-recombination process. Our studies have shown that the counterion plays a large role in the ESPT. Likewise, initiation of cationic polymerization is controlled by the counterion. NM6HQ perfluoroalkylsulfonates appear to be the first molecules reported which are capable of initiating aliphatic epoxide polymerization at room temperature through a proton transfer mechanism.