Siamese-Twin Porphyrin Goes Platinum: Group 10 Monometallic, Homobimetallic, and Heterobimetallic Complexes

Dorazio, Sarina J.; Vogel, Anastasia; Dechert, Sebastian; Nevonen, Dustin E.; Nemykin, Victor N.; Brückner, Christian; Meyer, Franc

doi:10.1021/acs.inorgchem.0c00714

Cited by 11 publications

(12 citation statements)

References 76 publications

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“…This is in good agreement with other 2 J Pt–C and 3 J Pt–C couplings reported in the literature for similar systems. , The 195 Pt NMR spectrum of Pt 2 L(PF 6 ) 2 shows one broad resonance at −3936 ppm (screened from −1800 to −6600 ppm). The chemical shift is within the expected range for Pt II complexes incorporating pyrazole or NHC ligands, e.g ., −2685 ppm for a topologically similar macrocyclic bis-pyrazolate complex reported by the Meyer group or −4494 ppm for a methylene-bridged macrocyclic tetra-NHC complex introduced by Kühn and co-workers . Notably, the 195 Pt NMR shift of Pt 2 L(PF 6 ) 2 is similar to the resonance of a mixed NHC/pyrazolate-ligated complex (−3778 ppm) reported by the Sicilia group …”

Section: Resultssupporting

confidence: 90%

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

Pickl

Pöthig

2021

Organometallics

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We present the synthesis, structural characterization, and photophysical properties of dinuclear Pd II and Pt II − NHC complexes Pd 2 L(PF 6 ) 2 and Pt 2 L(PF 6 ) 2 based on a macrocyclic calix[4]imidazolylidene[2]pyrazolate ligand obtained by in situ deprotonation of the tetraimidazolium salt H 6 L(PF 6 ) 4 . The Pt II congener was also prepared by transmetalation from previously published Ag I pillarplex Ag 8 L 2 (PF 6 ) 4 . NMR spectroscopy ( 1 H, 13 C, 195 Pt) combined with SC-XRD studies elucidated the structure of the Pd II and Pt II complexes in the solid state and in solution. The d 8 metal ions of both congeners are coordinated in a slightly distorted square-planar arrangement. Similar to the previously reported Ni II complex Ni 2 L(PF 6 ) 2 , the heavier metal homologues adopt a bent, saddle-shaped structure. As observed for structurally similar Pt II complexes in solution, bimetallic Pt 2 L(PF 6 ) 2 showed photoluminescence in the blue region. In the solid state, emission was observed at a similar energy with unusually short lifetimes compared to other monometallic Pt II complexes. DFT and TDDFT studies shed light on the nature of the most bathochromic transitions, suggesting a significant pyrazolate-and NHCcentered π−π* character.

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Section: Resultssupporting

confidence: 90%

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

Pickl

Pöthig

2021

Organometallics

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“…However, both pyrazoles are in an inverted position, pointing their nitrogen atoms inward. The result is the formation of two porphyrin-like square-planar N 4 -coordination sites that are linked through the pyrazole moieties. − …”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

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The replacement of one or more pyrrolic building block(s) of a porphyrin by a nonpyrrolic heterocycle leads to the formation of so-called pyrrole-modified porphyrins (PMPs), porphyrinoids of broad structural variability. The wide range of coordination environments (type, number, charge, and architecture of the donor atoms) that the pyrrole-modified frameworks provide to the central metal ions, the frequent presence of donor atoms at their periphery, and their often observed nonplanarity or conformational flexibility distinguish the complexes of the PMPs clearly from those of the traditional square-planar, dianionic, N 4 -coordinating (hydro)porphyrins. Their different coordination properties suggest their utilization in areas beyond which regular metalloporphyrins are suitable. Following a general introduction to the synthetic methodologies available to generate pyrrole-modified porphyrins, their general structure, history, coordination chemistry, and optical properties, this Review highlights the chemical, electronic (optical), and structural differences of specific classes of metalloporphyrinoids containing nonpyrrolic heterocycles. The focus is on macrocycles with similar "tetrapyrrolic" architectures as porphyrins, thusly excluding the majority of expanded porphyrins. We highlight the relevance and application of these metal complexes in biological and technical fields as chemosensors, catalysts, photochemotherapeutics, or imaging agents. This Review provides an introduction to the field of metallo-PMPs as well as a comprehensive snapshot of the current state of the art of their synthesis, structures, and properties. It also aims to provide encouragement for the further study of these intriguing and structurally versatile metalloporphyrinoids.

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“… − Generally, electron-rich aryl aldehydes gave better yields. Siamese-twin porphyrins have two divalent NNNN coordination sites, and a variety of mono- and bismetal complexes could be prepared readily. − The reactions of Siamese-twin porphyrin 436a with the corresponding metal reagents gave the bis-copper(II), nickel(II), palladium(II), and platinum(II) complexes 437a – d in 27–63% yields. When limited amounts of reagents were adopted, the mononickel(II), palladium(II), and platinum(II) complexes 438a – c were obtained in 21–83% yields.…”

Section: Confusion In Expanded Porphyrinsmentioning

confidence: 99%

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

Toganoh

Furuta

2022

Chem. Rev.

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Confusion is a novel concept of isomerism in porphyrin chemistry, delivering a steady stream of new chemistry since the discovery of N-confused porphyrin, a porphyrin mutant, in 1994. These days, the number of confused porphyrinoids is increasing, and confusion and associated fusion are found in various fields such as supramolecular chemistry, materials chemistry, biological chemistry, and catalysts. In this review, the birth and growth of confused porphyrinoids in the last three decades are described.

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Siamese-Twin Porphyrin Goes Platinum: Group 10 Monometallic, Homobimetallic, and Heterobimetallic Complexes

Cited by 11 publications

References 76 publications

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

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