This thesis presents work exploring the use of pressure as a tuning parameter for exploring the phase diagrams and properties of magnetically ordered insulators, to add understanding to several areas of current interest in condensed matter research. It shows the versatility of pressure as an experimental technique for exploring material properties free from complicating factors which arise with similar techniques such as chemical doping.

The properties of low-dimensional magnetic materials, and how these systems respond as they are pushed toward a more three-dimensional nature is explored through studies of both the crystal and magnetic structures of the family of quasi-two-dimensional magnetic insulators MPS3 (M = Fe, Ni, Mn). With previous work largely being specific to individual compounds, this thesis contributes to a more unified understanding of their properties. It shows that Ni and MnPS3 undergo similar structural transitions under pressure to those previous observed in FePS3, the highest pressure of which is linked to an insulator-to-metal transition in that system. Through record high-pressure neutron diffraction measurements, the evolution of the antiferromagnetic order in FePS3 through this metallisation is studied for the first time. In contradiction to previous indirect measurements, it is seen that magnetism persists into the metallic phase, with long range antiferromagnetism giving way to a previously unobserved short-range order. This work is relevant on a broader scale for numerous layered magnetic materials such as cuprate high temperature superconductors.

Secondly, pressure is used to explore the magnetocaloric properties of the antiferromagnet EuTiO3. Recent work has shown that this compound compares favourably to many materials commonly used in magnetic refrigeration. Measurements show that these properties are suppressed by the application of pressure and point towards the potential existence of a previously undiscussed transition in the material between 0.4 GPa and 0.5 GPa.