The controlled and targeted synthesis of new solid materials is still a challenge difficult to overcome. Slow diffusion rates and long diffusion lengths require long reaction times and high synthesis temperatures, resulting in limited control over the reaction pathway. The Modulated Elemental Reactants (MER) method uses compositionally modulated precursors with atomically thin elemental layers that form amorphous alloys upon annealing while maintaining composition modulation. In this amorphous intermediate, nucleation, not diffusion, control the formation of the product, enabling kinetic control of the reaction, and the synthesis of new metastable compounds, heterostructures with designed nanoarchitecture, and thin films with a high degree of texturing. This dissertation uses experimental and computational methods to investigate compounds synthesized by the MER method. Firth, the MER method is used to synthesize ferromagnetic CuCr2Se4 films that show a large degree of crystallographic alignment and interesting magnetic properties such as temperature-dependent easy axes and negative magnetoresistivity. The second part investigates ferecrystals, rotationally disordered members of the misfit layer compounds family. The MER method’s ability to control the nanoarchitecture of the products is used to synthesize a new type of structural isomers, allowing for the synthesis of thousands of ternary compounds using the same elements. Experimental methods are also used to monitor the formation of ferecrystalline compounds using [(SnSe)1+δ][VSe2] as a model system. Despite the vast number of compounds available, however, explaining the properties and stability of ferecrystals is still in its infancy. In the last part of this dissertation, ab initio methods are employed to investigate the components in our ferecrystals. Specifically, isolated layers of VSe2 with its structural distortions due to a charge density wave, SnSe with its thickness-dependent structures, and BiSe with its flexible lattice and anti-phase boundaries are investigated to complement experimental results. Some properties, such as the structural distortion in VSe2 and the different stabilities of BiSe layers, can be explained very well using this simplified model, but others, such as the structure of SnSe layers, are not exclusively determined by their dimensionality, underlining the complex nature of the interactions in ferecrystals. This dissertation includes previously published and unpublished co-authored material.