Fei Yen

Partial replacement of the organic linkers of metal-organic frameworks (MOFs) often optimizes their functionalities, however, accurate characterization of their molar ratios in many cases is challenging. This work presents a method of determining such linker ratios via measurements of the magnetic susceptibility of small quantities of powdered samples. The main presumption is taking the diamagnetic and paramagnetic contributions to the molar magnetic susceptibility of the two parent MOFs to be additive. To verify this, four examples are provided with commonly used MOFs to represent the cases when both parent MOFs are either paramagnetic or diamagnetic but with different linkers with the following systems: [MIL-101(Cr)-SO₃H]_1-δ[MIL-101(Cr)-NO₂]_δ, [EuMOF]_(1-δ)[EuPDCA]_δ, [UiO-66-COOH]_(1-δ)[UiO-66]_δ, and [MIL-101(Cr)F Free]_1-δ[MIL-53(Al)]_δ, where 1-δ: δ are the ratios to be determined. Depending on whether the systems were strictly paramagnetic, strictly diamagnetic or mixed, the experimental error of δ ranged between 0.00002 and 0.012, respectively. We expect the presented method to be widely employed since samples only need to be in powdered form and because there is a lack of characterization tools in the area of MOF linker ratios. The presented method is also applicable to resolving the ratios of mixed ordinary paramagnetic systems as well as other types of nonmagnetic composite materials such as tapes, zeolites and thin films.

Reorienting polyatomic ions such as NH4+ and NO3- exhibit weak magnetic fields because the ions at the extremities trace out current loops; if the periodic reorientations become long-range ordered (i.e. gearing of neighboring NO3-), then the magnetic susceptibility should exhibit a unique signature along the different crystallographic axes. For the case of ammonium nitrate NH4NO3, we report the presence of two successive sharp steps in the molar magnetic susceptibility along the a- and b-axes upon crossing its order-disorder phase transition (from phase IV to phase II). We suggest the first step pertains to the NO3- planes shifting away from facing only along the b-axis and onto the a-axis by 45°. The second step is attributed to the disordering (ungearing) of the NH4+ and NO3-. In contrast, only one step was observed in the magnetic susceptibility along the c-axis and its large magnitude suggest the NO3- remain weakly correlated even in phase I at 400 K. We also find evidence that the NH4+ become magnetically ordered (geared) along the c-axis only until phase V. The approach employed in this work can be extended to experimentally study the lattice dynamics of other solids possessing planar ions such as amphidynamic crystals.

Many solid crystals exhibit a structural phase transition where a subset of its ions or entire molecules become orientationally ordered. As to why such ordering occurs remains mostly unresolved. We consider the extremely weak magnetic elements arising from the reorientations of the molecules experiencing mutual resonance to play the chief role. Two new features are identified in d-camphor: (1) the magnetic susceptibility abruptly changes when crossing the order–disorder phase transition at TII–III = 239.8 K during cooling and at TIII–II = 245.2 K during warming and (2) the complex dielectric constant exhibits two successive discontinuities only 0.2 K apart near the critical temperatures when the sweeping rate is only 0.1 K/min. We discuss how the change in entropy associated with order–disorder transitions in plastic crystals represents temporal changes rather than spatial changes in the system. Our findings may be extended to study why many other crystalline solids exhibit orientational ordering and irreversibility.

By exploiting the additive nature of the molar magnetic susceptibility χ_Mol and molar mass m_Mol, the doping concentration δ of diamagnetic mixed solids can be resolved to ∼100 parts with only 20 mg of powdered samples. Eight examples are provided.

The β and γ phases of methylammonium chloride CH₃NH₃Cl and methylammonium bromide CH₃NH₃Br are identified to be ferroelectric via pyroelectric current and dielectric constant measurements.