Guest-induced magnetic exchange in paramagnetic [M₂L₄]⁴⁺ coordination cages

Abstract

Paramagnetic complexes that show magnetically switchable properties show promise in a number of applications. A significantly underdeveloped approach is the use of metallocages, whose magnetic properties can be modulated through...

A graceful break-up: serendipitous self-assembly of a ferromagnetically coupled [NiII14] wheel

“…S3, red curve).The narrow range of values obtained can be attributed to the presence of similar structural parameters for each metal ion, with the relatively small Ni-µ-O/Cl-Ni angles resulting in ferromagnetic exchange (Table S4). 19 To further explore the origin of the sign and magnitude of these interactions we have performed overlap integral calculations [20][21][22] between the singly occupied molecular orbitals (SOMOs) of the Ni II ions in a bimetallic model (1D) created from 1 (Fig. S6).…”

A ferromagnetically coupled pseudo-calixarene [Co16] wheel that self-assembles as a tubular network of capsules

“…This method is known to reproduce experimental magnetic exchange values for systems with weak intramolecular magnetic exchange interactions (J ≤ 10 cm -1 ). 2 The hybrid B3LYP functional 3 has been used together with the TZV basis set for Co, SVP basis set for Zn, O and SV basis set for C and H atoms. 4 We have employed Noodleman's broken symmetry methodology.…”

“…1 In the field of molecular magnetism, molecular wheels of 3d transition metals came into prominence in the late 1980s and early 1990s with the publication of [Cr III 8] and [Fe III 10]. 2 The former has inspired the development of a large family of homo-and heterometallic Cr wheels including the first examples of odd-numbered wheels that display topological frustration, with potential as quantum bits in information processing. 3 The latter, and other antiferromagnetically coupled even-membered wheels, are characterised by a diamagnetic spin ground state and display interesting quantum phenomena and spin dynamics, including tunneling of the Néel vector, 4 spin-multiplet mixing effects 5 and magnetic level repulsions.…”

Selective Supramolecular Recognition of Nitroaromatics by a Fluorescent Metal–Organic Cage Based on a Pyridine-Decorated Dibenzodiaza-Crown Macrocyclic Co(II) Complex

“…The most common M 2 L 4 cages employ square planar Pd­(II) centers and pyridine ligands. However, other transition metals such as platinum, − cobalt, − copper, − zinc, ,,, and nickel ,, have also been exploited. MOCs are capable of adsorbing reactive molecules and various chemical guests. − …”