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4. Heteroleptic Tripalladium(II) Cages

Author

Findlay, James A., primary, Patil, Komal M., additional, Gardiner, Michael G., additional, MacDermott‐Opeskin, Hugo I., additional, O'Mara, Megan L., additional, Kruger, Paul E., additional, and Preston, Dan, additional

Published
2022
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7. Heteroleptic Tripalladium(II) Cages.

Author

Findlay, James A., Patil, Komal M., Gardiner, Michael G., MacDermott‐Opeskin, Hugo I., O'Mara, Megan L., Kruger, Paul E., and Preston, Dan

Subjects
*LIGANDS (Chemistry), *PALLADIUM, *GEOMETRY
Abstract

There is a concerted attempt to develop self‐assembled metallo‐cages of greater structural complexity, and heteroleptic PdII cages are emerging as prime candidates in these efforts. Most of these are dinuclear: few examples of higher nuclearity have been reported. We demonstrate here a robust method for the formation of tripalladium(II) cages from the 2 : 3 : 3 combination of a tritopic ligand, PdII, and a selection of ditopic ligands of the correct size and geometry. [ABSTRACT FROM AUTHOR]

Published
2022
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12. Effect of anion on Ag(I) meso-helical chains formed with 4,4'-dipyridyl ketone: solvent versus anion bridging and anion effects on the strength of ligand binding.

Author

Patil, Komal M., Cameron, Scott A., Moratti, Stephen C., and Hanton, Lyall R.

Subjects
*SINGLE crystals, *ANION synthesis, *X-ray diffraction, *COORDINATION polymers synthesis, *PYRIDYL compounds
Abstract

The synthesis and characterisation by IR spectroscopy and elemental analysis of ten new Ag(I)-L complexes are described. Of these complexes, nine are characterised by single crystal X-ray diffraction: {[Ag(L)](CF3SO3)·½H2O}∞ (1), {[Ag(L)](ClO4)·1/2H2;)∞ (2), {[Ag2(L)2(CH3CN)](ClC4)2·H2O)∞ (3), {[Ag2(L)2(CH3CN)2](ClO4)2·CH3CN)∞ (4), {[Ag2(L)2(CH3CN)2](PF6)2·2CH3CN)∞ (5), {[Ag(L)2](CF3SO3)4/2H2OL (6), {[Ag(L)2](BF4)∞(7), {[Ag(L)2](PF6))∞ (8) and {[Ag(L)2](PF6)·2CH3CN)∞ (9). The primary structures of 1-6 were meso-helical one-dimensional (1D) polymers, while 7 was a helical 1D polymer and 8 and 9 were (4,4) networks. Complexes 1-5 possessed 1:1 metal-to-ligand (M: L) ratios, while complexes 6-9 possessed 1:2 M: L ratios. The meso-helical chains of complexes 1 and 2 were di-μ-bridged at the Ag(I) nodes by the counteranions CF3SC>3- and CIO4-, respectively, while the meso-helical chains of complexes 3-5 were di-μ-bridged at the Ag(I) nodes by the CH3CN molecules. The effect of counteranions and solvent molecules on delicate anion-Ag, π-π-stacking and argentophilic interactions was studied through complexes 1-5. The 1D chains of complexes 6 and 7 possessed monodentate L ligand side arms. The uncoordinated N-donors of these side arms were inclined towards the Ag(I) centre of the adjacent chains and demonstrated narrower Ag-Npy-Cg(pyridyl) angles. In the case of complexes 8 and 9, wider Ag-Npy-Cg(pyridyl) angles and stronger N⋯Ag interactions resulted in (4,4) nets. The effects of the size and the nature of the counteranions on the topology were studied through complexes 6-9. [ABSTRACT FROM AUTHOR]

Published
2014
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13. Breaking the trade-off between selectivity and adsorption capacity for gas separation

Author

Kumar, Naveen, Mukherjee, Soumya, Harvey-Reid, Nathan C., Bezrukov, Andrey A., Tan, Kui, Martins, Vinicius, Vandichel, Matthias, Pham, Tony, van Wyk, Lisa M., Oyekan, Kolade, Kumar, Amrit, Forrest, Katherine A., Patil, Komal M., Barbour, Leonard J., Space, Brian, Huang, Yining, Kruger, Paul E., Zaworotko, Michael J., Kumar, Naveen, Mukherjee, Soumya, Harvey-Reid, Nathan C., Bezrukov, Andrey A., Tan, Kui, Martins, Vinicius, Vandichel, Matthias, Pham, Tony, van Wyk, Lisa M., Oyekan, Kolade, Kumar, Amrit, Forrest, Katherine A., Patil, Komal M., Barbour, Leonard J., Space, Brian, Huang, Yining, Kruger, Paul E., and Zaworotko, Michael J.

Abstract

peer-reviewed, The trade-off between selectivity and adsorption capacity with porous materials is a major roadblock to reducing the energy foot-print of gas separation technologies. To address this matter, we report herein a systematic crystal engineering study of C2H2 removal from CO2 in a family of hybrid ultramicroporous materials (HUMs). The HUMs are composed of the same organic linker ligand, 4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, pypz, three inorganic pillar ligands, and two metal cations, thereby affording six isostructural pcu topology HUMs. All six HUMs exhibited strong binding sites for C2H2 and weaker affinity for CO2. The tuning of pore size and chemistry enabled by crystal engineering resulted in benchmark C2H2/CO2 separation performance. Fixed-bed dynamic column breakthrough experiments for an equimolar (v/v = 1:1) C2H2/CO2 binary gas mixture revealed that one sorbent, SIFSIX-21-Ni, was the first C2H2 selective sorbent that combines exceptional separation selectivity (27.7) with high adsorption capacity (4 mmol.g-1)

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