Catalytic and topological aspects of Schiff base supported 3d-4f polynuclear coordination complexes

The work presented in this thesis deals with the employment of Schiff base ligands used to synthesise novel 3d-4f polynuclear coordination clusters (PCCs) and the investigation into their potential magnetic, luminescent and catalytic properties. Chapter one provides a general introduction to the chemistry described in the thesis. It includes a general overview of 3d-4f PCC chemistry and the applications of these materials and previous synthetic strategies for the preparation of Schiff base PCCs. A rationale is presented for the ligands employed in the thesis and a synthetic strategy is devised for the synthesis of specific materials. The initial chapters are focused on the synthesis of 3d-4f PCCs with novel core topologies and the study of their magnetic properties. Several novel series of 3d-4f PCCs are presented with unique core topologies which are previously unobserved in 3d-4f PCC chemistry. In addition, some of the presented PCCs display single-molecule magnet (SMM) properties or a significant magnetocaloric effect (MCE). Chapter five bridges synthetic aspects discussed in the previous chapters, with a synthetic study targeting 3d-4f PCCs with a defect dicubane core (2,3M4-1) and introduces the term “isoskeletal” to describe PCCs which possess the same topology or related organic structures with the same host framework but different guests. Chapters seven to nine are focused on the development of a well characterised isoskeletal family of 3d-4f PCCs with a defect dicubane core and the investigation of their potential catalytic properties in a range of organic reactions including Michael Addition, Friedel-Crafts alkylations and multicomponent reactions. Characterisation of the 3d-4f PCCs is emphasised and verifies the stability of the 2,3M4-1 core in solution. An attempt at understanding the catalytic system and mechanistic aspects is undertaken, which is not explored in previously reported 3d-4f PCC co-operative catalysis. Chapter ten provides an overall conclusion to the work presented in the thesis, whilst highlighting the contributions of this work to the reported literature

Synthesis, characterization, magnetic properties, and topological aspects of isoskeletal heterometallic hexanuclear Co II 4 Ln III 2 coordination clusters possessing 2,3,4M6-1 Topology

The reaction of (E)-2-(2-hydroxy-3-methoxybenzylideneamino)phenol (H2L1) with Co(NO3)26H2O and LnCl3x(H2O) afforded a family of hexanuclear heterometallic coordination clusters (CCs) formulated as [CoII4LnIII2(µ3-OH)2(L1)4Cl2(NO3)2(MeOH)4] 3(Et2O) where Ln is Y (1), Gd (2), Dy (3), and Tb (4). All the compounds are stable in solution as confirmed by ESI-MS studies. The compounds can be described as twisted boat-like and possess a 2,3,4M6–1 topology. The reaction of (E)-2-(5-bromo-2-hydroxy-3-methoxybenzylideneamino)phenol (H2L2) with Co(NO3)26H2O and DyCl3x(H2O) afforded [CoII4DyIII2(µ3-OH)2(L2)4Cl2(NO3)2(MeOH)4] (5), which is isoskeletal to compounds 1–4. Magnetic studies performed over the temperature range 1.8–300 K show that compound 3 undergoes slow magnetic relaxation

Isoskeletal Schiff base polynuclear coordination clusters: synthetic and theoretical aspects

This work addresses and enlightens synthetic aspects derived from our effort to systematically construct isoskeletal tetranuclear coordination clusters (CCs) of the general formula [TR2Ln2(LX)4(NO3)2(solv)2] possessing a specific defected dicubane topology, utilizing various substituted Schiff base organic ligands (H2LX) and NiII/CoII and Dy(OTf)3 salts. Our synthetic work is further supported by DFT studies

Dinuclear Lanthanide (III) coordination polymers in a domino reaction

A systematic study was performed to further optimise the catalytic room-temperature synthesis of trans-4,5- diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. For this purpose, a series of dinuclear lanthanide (III) coordination polymers were synthesised using a dianionic Schiff base and their catalytic activities were investigated

Tetranuclear Zn2Ln2 coordination clusters as catalysts in Petasis borono-Mannich multicomponent reaction

We report herein for the first time the efficiency of heteronuclear Zn/Ln coordination clusters (CCs) as catalysts for the multicomponent Mannich-type condensation that involves amines, aldehydes and boronic acids, known as Petasis borono-Mannich (RBR) reaction. The reaction proceeds in very good to excellent yields (84-98%, 17 products) at room temperature with catalyst loadings as low as 1.0 mol%

News Representation and Sense of Belonging Among Multicultural Audiences

This study seeks to understand the role of representation in news media, trust in news, and participation in multicultural audiences' sense of belonging to society. A multimodal survey combining online, CATI, and CAPI methods was conducted in Australia at the end of 2021 and early 2022 (N = 1,084). The top five non-English language communities in Australia (Arabic, Cantonese, Italian, Mandarin, and Vietnamese) were included in the survey, of which n = 851 were born overseas. The findings reveal a significant link between the perception of sufficient representation in Australian news media, trust in news, confidence to participate in society, and sense of belonging. When multicultural audiences see themselves fairly and adequately represented in the news, they are more likely to trust the news and participate in the community by discussing the news and current affairs. This, in turn, leads to a stronger sense of belonging to society. We also found confidence in English and time spent in Australia were important factors contributing to perceptions of representation. While the length of stay has a positive impact on the perception of representation among those with high confidence in English, this perception is significantly lower among those who have lower confidence. This result confirms the significant role language proficiency plays in migrants' experiences in the host country

Tetranuclear CuII2DyIII2 coordination cluster as Suzuki (C–C) coupling reaction promoter

The air stable and high yielding tetranuclear coordination cluster [CuII2DyIII2L4(NO3)2(CH3CN)2]·2(CH3CN) promotes the Suzuki coupling reaction of phenylboronic acid with substituted aryl halides in environmentally benign conditions

Crystalline azobenzene composites as photochemical phase-change materials

Crystalline binary mixtures of azobenzene and 4-methoxyazobenzene are reported and form photochemical phase change materials that possess working temperatures in the range of −58 °C to 31 °

Long-Term Solar Energy Storage under Ambient Conditions in a MOF-Based Solid–Solid Phase-Change Material

This paper demonstrates a metal−organic framework (MOF) containing photoswitches within the pores as a hybrid solar thermal fuel (STF) and solid−solid phase-change material (ss-PCM). A series of azobenzene-loaded MOFs were synthesized with the general formula Zn2(BDC)2(DABCO)(AB)x (BDC = 1,4-benzenedicarboxylate, DABCO = 1,4- diazabicyclo[2.2.2]octane, AB = azobenzene, where x = 1.0, 0.9, 0.5, 0.3), herein named 1⊃AB1.0, 1⊃AB0.9, 1⊃AB0.5, and 1⊃AB0.3 respectively. X-ray powder diffraction, solid-state NMR, and density functional theory calculations were used to explore in detail the structural changes of the host framework that take place upon loading with the AB guest molecules. Differential scanning calorimetry measurements reveal a reversible phase change, which is absent from the evacuated framework. Upon irradiation with 365 nm light, 40% of the AB guests converted from the trans to the higher-energy cis isomeric form in 1⊃AB1.0. The energy stored within the metastable cis isomers is released upon heating and balances the endotherm associated with the phase transition. However, the exotherm associated with the phase transition is retained upon cooling, resulting in a net energy release over a full heating−cooling cycle. The maximum energy density is observed for the fully loaded composite 1⊃AB1.0, which releases 28.9 J g−1. In addition, the cis-AB guests in this composite showed negligible thermal reconversion during 4 months at ambient temperature, with an estimated energy storage half-life of 4.5 years. Further development of MOF-based STF-ss-PCMs could lead to applications for solar energy conversion and storage, and thermal management