Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions

Thomas, Kolle E.; Desbois, Nicolas; Conradie, Jeanet; Teat, Simon J.; Gros, Claude P.; Ghosh, Abhik

doi:10.1039/c9ra09228e

Cited by 14 publications

(12 citation statements)

References 64 publications

(46 reference statements)

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“…The DPP ligand scaffold was first described as being redox-active in 2012 after the synthesis of cobalt- and nickel-DPP complexes. 12 Hereafter, the redox activity was further studied in Mn, 13 Pt, 14 Cu, 15 and Au 16 complexes. Catalytic applications have been reported for the Ti, Zr, Gn, and Sn complexes (copolymerization of epoxides with CO 2 ) and Cu (aerobic alcohol oxidation).…”

Section: Introductionmentioning

confidence: 99%

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex

Leest

Stroek

Siegler³

et al. 2020

Inorg. Chem.

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The influence of a redox-active ligand on spin-changing events induced by the coordination of exogenous donors is investigated within the cobalt complex [Co II (DPP· 2– )] , bearing a redox-active DPP 2– ligand (DPP = dipyrrin-bis( o , p -di- tert -butylphenolato) with a pentafluorophenyl moiety on the meso -position. This square-planar complex was subjected to the coordination of tetrahydrofuran (THF), pyridine, t BuNH 2 , and AdNH 2 (Ad = 1-adamantyl), and the resulting complexes were analyzed with a variety of experimental (X-ray diffraction, NMR, UV–visible, high-resolution mass spectrometry, superconducting quantum interference device, Evans’ method) and computational (density functional theory, NEVPT2-CASSCF) techniques to elucidate the respective structures, spin states, and orbital compositions of the corresponding octahedral bis-donor adducts, relative to [Co II (DPP· 2– )] . This starting species is best described as an open-shell singlet complex containing a DPP· 2– ligand radical that is antiferromagnetically coupled to a low-spin ( S = 1 / 2 ) cobalt(II) center. The redox-active DPP n – ligand plays a crucial role in stabilizing this complex and in its facile conversion to the triplet THF adduct [Co II (DPP· 2– )(THF) 2 ] and closed-shell singlet pyridine and amine adducts [Co III (DPP 3– )(L) 2 ] (L = py, t BuNH 2 , or AdNH 2 ). Coordination of the weak donor THF to [Co II (DPP· 2– )] changes the orbital overlap between the DPP· 2– ligand radical π-orbitals and the cobalt(II) metalloradical d-orbitals, which results in a spin-flip to the triplet ground state without changing the oxidation states of the metal or DPP· 2– ligand. In contrast, coordination of the stronger donors pyridine, t BuNH 2 , or AdNH 2 induces metal-to-ligand single-electron transfer, resulting in the formation of low-spin ( S = 0) cobalt(III) complexes [Co III (DPP 3– )(L) 2 ] conta...

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Section: Introductionmentioning

confidence: 99%

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex

Leest

Stroek

Siegler³

et al. 2020

Inorg. Chem.

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“…105). [289][290][291] Dipyrrin-bisphenol is a tetradentate ligand, like corrole and porphyrin, and interestingly, its chemical structure can be seen as the combination of half a salen unit and half of a porphyrin macrocycle (Fig. 105).…”

Section: Dipyrrin-bisphenol: Corrole Analogsmentioning

confidence: 99%

“…What makes the dipyrrin-bisphenol ligand closer to a corrole (and not a porphyrin) is that it presents, like corrole, a formal À3 charge and this molecule is able to coordinate quite a large variety of nonmetal or metal ions such as boron, 292 manganese, 291 cobalt, 290 gold. 289 Dipyrrin-bisphenol is a 12 p-conjugated system with only one meso-position and 4 beta-pyrrolic positions. As in the case of the corrole macrocycle, 8,293-298 some innocent or noninnocent character of the ligand can be encountered, depending on the nature of the metal or non-metal ion.…”

Section: Dipyrrin-bisphenol: Corrole Analogsmentioning

confidence: 99%

Corroles at work: a small macrocycle for great applications

2022

Self Cite

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“…Various original N 2 O 2 dipyrrin compounds complexed with transition metals, such as Ti, 128 Zr, 128 Mn, [131][132][133] Co, [134][135][136] Ni, 134,137 Cu, 138,139 Au, 140 Ge, 128,129 and Sn 128 , have been synthesized and structurally characterized, although the emission properties of these complexes have not been reported. They, however, exhibited various interesting properties and functions, such as catalytic activity, redox activity, chiroptical properties, and pharmaceutically relevant properties.…”

Section: Other N 2 O 2 Dipyrrin Complexes With Unique Properties and mentioning

confidence: 99%

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

Chiba¹,

Nakamura²,

Matsuoka³

et al. 2020

Synlett

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The dipyrrin–metal complexes and especially the boron complex 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) have recently attracted considerable attention because of their interesting properties and possible applications. We have developed two unique and useful ways to extend versatility and usefulness of the dipyrrin complexes. The first one is the linear and macrocyclic oligomerization of the BODIPY units. These arrangements of the B–F moieties of the oligomerized BODIPY units provide sophisticated functions, such as unique recognition ability toward cationic guest, associated with changes in the photophysical properties by utilizing unprecedented interactions between the B–F and a cationic species. The second one is introduction of additional ligating moieties into the dipyrrin skeleton. The multidentate N2Ox dipyrrin ligands thus obtained form a variety of complexes with 13 and 14 group elements, which are difficult to synthesize using the original N2 dipyrrin derivatives. Interestingly, these unique complexes exhibit novel structures, properties, and functions such as guest recognition, stimuli-responsive structural conversion, switching of the optical properties, excellent stability of the neutral radicals, etc. We believe that these multifunctional dipyrrin complexes will advance the basic chemistry of the dipyrrin complexes and develop their applications in the materials and medicinal chemistry fields.1 Introduction2 Linear Oligomers of Boron–Dipyrrin Complexes3 Cyclic Oligomers of Boron–Dipyrrin Complexes4 A Cyclic Oligomer of Zinc–Dipyrrin Complexes5 Group 13 Element Complexes of N2Ox Dipyrrins6 Chiral N2 and N2Ox Dipyrrin Complexes7 Group 14 Element Complexes of N2O2 Dipyrrins8 Other N2O2 Dipyrrin Complexes with Unique Properties and Functions9 Conclusion

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Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions

Abstract: The first gold dipyrrin-bisphenolates have been synthesized. Like their corrole analogues, they exhibit AuIII–L3− ground states, providing rare innocent paradigms for a class of complexes that commonly occur as metalloradicals.

Cited by 14 publications

References 64 publications

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex

Corroles at work: a small macrocycle for great applications

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

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