The creation of ordered arrays of
qubits that can be interfaced
from the macroscopic world is an essential challenge for the development
of quantum information science (QIS) currently being explored by chemists
and physicists. Recently, porous metal–organic frameworks (MOFs)
have arisen as a promising solution to this challenge as they allow
for atomic-level spatial control of the molecular subunits that comprise
their structures. To date, no organic qubit candidates have been installed
in MOFs despite their structural variability and promise for creating
systems with adjustable properties. With this in mind, we report the
development of a pillared-paddlewheel-type MOF structure that contains
4,7-bis(2-(4-pyridyl)-ethynyl) isoindoline N-oxide
and 1,4-bis(2-(4-pyridyl)-ethynyl)-benzene pillars that connect 2D
sheets of 9,10-dicarboxytriptycene struts and Zn2(CO2)4 secondary binding units. The design allows for
the formation of ordered arrays of reorienting isoindoline nitroxide
spin centers with variable concentrations through the use of mixed
crystals containing the secondary 1,4-phenylene pillar. While solvent
removal causes decomposition of the MOF, magnetometry measurements
of the MOF containing only N-oxide pillars demonstrated
magnetic interactions with changes in magnetic moment as a function
of temperature between 150 and 5 K. Variable-temperature electron
paramagnetic resonance (EPR) experiments show that the nitroxides
couple to one another at distances as long as 2 nm, but act independently
at distances of 10 nm or more. We also use a specially designed resonance
microwave cavity to measure the face-dependent EPR spectra of the
crystal, demonstrating that it has anisotropic interactions with impingent
electromagnetic radiation.