Photochemical hydrogen evolution from water by a 1D-network of octahedral Ni<sub>6</sub>L<sub>8</sub> cages

Kumar, Kilaparthi Sravan; Mane, Vishwanath S.; Yadav, Ashok; Kumbhar, Avinash S.; Boomishankar, Ramamoorthy

doi:10.1039/c9cc06286f

Cited by 12 publications

(5 citation statements)

References 32 publications

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“…So far, structural studies of the coordination chemistry of tris(3-pyridyl) ligands containing the heavier main-group elements have been limited to the very recently prepared Li[EtAl(3-py) 3 ] (whose coordination chemistry was not explored) and those of Group 14. In accordance with expectations, the MeSi(3-py) 3 − and (air-stable) PhSn(3-py) 3 ligands have been shown to form cage and 1D or 2D network arrangements with metal ions. Particularly relevant to the current study is the cage [{PhSn(3-py) 3 } 4 (Cu·MeCN) 4 (⊂PF 6 )] 3+ , formed by the coordination of CuPF 6 by PhSn(3-py) 3 in acetonitrile (MeCN) because of the templating effect of PF 6 – .…”

Section: Introductionsupporting

confidence: 86%

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

et al. 2021

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The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py) 3 ] and [Bi(3-py) 3 ] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal–organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF 6 – , SbF 6 – , and OTf – ), composed of a cationic substructure of rhombic cage (M) 4 (L) 4 units linked by Sb/Bi–M bonding. The greater Lewis acidity of Bi compared to Sb can, however, allows anion···Bi interactions to overcome Bi–metal bonding in the case of BF 4 – , leading to collapse of the MOF structure (which is also seen where harder metals like Li + are employed). This study therefore provides insight into the way in which the electronic effects of the bridgehead atom in these ligand systems can impact their supramolecular chemistry.

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Section: Introductionsupporting

confidence: 86%

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

et al. 2021

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“…125 Changing the metal node to nickel led to increased activity of the resulting cage [Ni 6 7 8 ] (C6b). 126 As in the previous system, the authors state that the polypyridyl silane ligands 7 stabilize low oxidation states on the nickel ions and act as redox-active functions to assist the PCET process. In contrast to the Co(II) analogue, C6b is significantly more stable and showed to be active for 69 h under irradiation in photocatalytic conditions, with a maximum TOF of 41 h −1 and TON of 2824.…”

Section: Proton Reductionmentioning

confidence: 86%

“…This is beneficial, as PCET lowers the thermodynamic barrier by avoiding charge accumulation . Changing the metal node to nickel led to increased activity of the resulting cage [Ni 6 7 8 ] ( C6b ) . As in the previous system, the authors state that the polypyridyl silane ligands 7 stabilize low oxidation states on the nickel ions and act as redox-active functions to assist the PCET process.…”

Section: Coordination Cages For Artificial Photosynthesismentioning

confidence: 99%

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

et al. 2023

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Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable energy supply to light driven chemistry. From a chemical perspective, excited states generated by light make thermodynamically uphill reactions possible, which forms the basis for energy storage into fuels. In addition, with light, open-shell species can be generated which open up new reaction pathways in organic synthesis. Crucial are photosensitizers, which absorb light and transfer energy to substrates by various mechanisms, processes that highly depend on the distance between the molecules involved. Supramolecular coordination cages are well studied and synthetically accessible reaction vessels with single cavities for guest binding, ensuring close proximity of different components. Due to high modularity of their size, shape, and the nature of metal centers and ligands, cages are ideal platforms to exploit preorganization in photocatalysis. Herein we focus on the application of supramolecular cages for photocatalysis in artificial photosynthesis and in organic photo(redox) catalysis. Finally, a brief overview of immobilization strategies for supramolecular cages provides tools for implementing cages into devices. This review provides inspiration for future design of photocatalytic supramolecular host−guest systems and their application in producing solar fuels and complex organic molecules.

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“…Despite increasing interest in this area, the elaboration of this type of ligand using extended N-donor polyaromatic donor groups has been largely ignored as a means of modifying the coordination character. The first example of this type containing a heavier element bridgehead was MeSi(3-qy) 3 (qy = quinolyl), − while the first example possessing a fully metallic bridgehead atom was only reported recently. In [{EtAl(2-Me-8-qy) 3 }Li] (containing the anion [EtAl(2-Me-8-qy) 3 ] − ), the Li + cation has an unusual trigonal planar, three-coordinate arrangement due to the combination of steric effects and the geometric constraints imposed by the orientation of the donor quinolyl N atoms (Figure c) .…”

Section: Introductionmentioning

confidence: 99%

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

et al. 2023

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The substitution of heavier, more metallic atoms into classical organic ligand frameworks provides an important strategy for tuning ligand properties, such as ligand bite and donor character, and is the basis for the emerging area of main-group supramolecular chemistry. In this paper, we explore two new ligands [E(2-Me-8-qy)3] [E = Sb (1), Bi (2); qy = quinolyl], allowing a fundamental comparison of their coordination behavior with classical tris(2-pyridyl) ligands of the type [E′(2-py)3] (E = a range of bridgehead atoms and groups, py = pyridyl). A range of new coordination modes to Cu+, Ag+, and Au+ is seen for 1 and 2, in the absence of steric constraints at the bridgehead and with their more remote N-donor atoms. A particular feature is the adaptive nature of these new ligands, with the ability to adjust coordination mode in response to the hard–soft character of coordinated metal ions, influenced also by the character of the bridgehead atom (Sb or Bi). These features can be seen in a comparison between [Cu2{Sb(2-Me-8-qy)3}2](PF6)2 (1·CuPF6) and [Cu{Bi(2-Me-8-qy)3}](PF6) (2·CuPF6), the first containing a dimeric cation in which 1 adopts an unprecedented intramolecular N,N,Sb-coordination mode while in the second, 2 adopts an unusual N,N,(π-)C coordination mode. In contrast, the previously reported analogous ligands [E(6-Me-2-py)3] (E = Sb, Bi; 2-py = 2-pyridyl) show a tris-chelating mode in their complexes with CuPF6, which is typical for the extensive tris(2-pyridyl) family with a range of metals. The greater polarity of the Bi–C bond in 2 results in ligand transfer reactions with Au(I). Although this reactivity is not in itself unusual, the characterization of several products by single-crystal X-ray diffraction provides snapshots of the ligand transfer reaction involved, with one of the products (the bimetallic complex [(BiCl){ClAu2(2-Me-8-qy)3}] (8)) containing a Au2Bi core in which the shortest Au → Bi donor–acceptor bond to date is observed.

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Photochemical hydrogen evolution from water by a 1D-network of octahedral Ni₆L₈ cages

Abstract: An efficient photochemical hydrogen evolution reaction in water supported by a 1D-coordination network of octahedral cages is demonstrated with high turnover numbers.

Cited by 12 publications

References 32 publications

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

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Photochemical hydrogen evolution from water by a 1D-network of octahedral Ni6L8 cages

Abstract: An efficient photochemical hydrogen evolution reaction in water supported by a 1D-coordination network of octahedral cages is demonstrated with high turnover numbers.

Cited by 12 publications

References 32 publications

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

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Photochemical hydrogen evolution from water by a 1D-network of octahedral Ni₆L₈ cages