Porphyrinoid f-Element Complexes

Brewster, James T.; Zafar, Hadiqa; Root, Harrison D.; Sessler, Jonathan L.

doi:10.1021/acs.inorgchem.9b00884

Cited by 29 publications

(29 citation statements)

References 195 publications

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“…Expanded porphyrins [ 7 , 22 , 23 , 24 ] have gained remarkable attention due to their interesting and versatile features, such as diverse π-conjugation pathways owing to flexible structures [ 25 ], near- infrared (NIR) absorption/emission [ 26 ], facile interconversion between multiple redox states [ 27 ], and multi-metal coordination cavities for various divalent and trivalent metal ions ( Figure 1 ) [ 22 , 28 ]. Beyond the study of these unique properties and their applications, the interest in expanded porphyrins has been focused on exploring the limits to which the classic Hückel definition of aromaticity may be applied.…”

Section: Introductionmentioning

confidence: 99%

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

2020

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Corroles and hexaphyrins are porphyrinoids with great potential for diverse applications. Like porphyrins, many of their applications are based on their unique capability to interact with light, i.e., based on their photophysical properties. Corroles have intense absorptions in the low-energy region of the uv-vis, while hexaphyrins have the capability to absorb light in the near-infrared (NIR) region, presenting photophysical features which are complementary to those of porphyrins. Despite the increasing interest in corroles and hexaphyrins in recent years, the full potential of both classes of compounds, regarding biological applications, has been hampered by their challenging synthesis. Herein, recent developments in the synthesis of corroles and hexaphyrins are reviewed, highlighting their potential application in photodynamic therapy.

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Section: Introductionmentioning

confidence: 99%

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

2020

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“…For further information, the reader can refer to a recent review which covers the field comprehensively. 153 Even though there are many other types of expanded porphyrins, 153 only grandephyrin 154 showed successful complexation with lutetium: bis(trimethylsilyl)amide of Lu III was added into the free-base macrocycle in THF solution and in the absence of water and oxygen. Unfortunately, the resulting Lu IIIgrandephyrin adduct was unstable and slowly decomposed upon exposure to air and moisture (Fig.…”

Section: Complexation With Expanded Porphyrins (Texaphyrins)mentioning

confidence: 99%

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

Chan

Xie

et al. 2021

Chem. Soc. Rev.

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“…follows CHON principle). 9 In this regard, macrocycles such as crown ethers, 10,11 calixarenes, 12 cucurbiturils, 13 pyrrolebased expanded porphyrins [14][15][16] has gained popularity as promising candidates.…”

Section: Introductionmentioning

confidence: 99%

“…Experimentally, it has been perceived that the modulation of cavity size by expanding the porphyrin ring can make it accessible for complexation with f-block elements. 14,15 Recent reports on synthesis of series of An(IV) complexes with a class of expanded porphyrins has made a strong case on its applicability in actinide extraction. While these ligands contain soft N as the donor center for such task, ligands such as salens, 17 pyrrophen utilizes both soft N and hard O as the donor atoms to bind hard uranyl cation.…”

Section: Introductionmentioning

confidence: 99%

Role of O Substitution in Expanded Porphyrins on Uranyl Complexation: Orbital- and Density-Based Analyses

2021

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The need for efficient macrocyclic ligands that can sequester U(VI) has gained immense importance due to the increased applications of U(VI) in various sectors, including but not limited to nuclear energy. Structural attributes such as number and type of donor centers ("hard" and "soft") of ligands are essentially the key components for providing the adequate bonding scenario for uranyl. Beside hard or soft-donor-based binding cavity, the mixeddonor ligands are also finding popularity for achieving optimized performances. However, many aspects are still unknown about how and at what extent the ratio of hard-to-soft donor centers tune the bonding attributes with uranyl. Moreover, a consensus is yet to be reached on the nature and role of underlying covalent interaction between U and donors upon complexation, particularly in the mixed-donor ligand environment. In this work, using relativistic density functional theory (DFT), we attempted to address these important issues by systematically investigating the impact on the bonding characteristics of uranyl ion and an expanded porphyrin, viz. sapphyrin with increasing number of 'O' substitution at the cavity. Our results suggest that in the O-substituted sapphyrin variants, UO 2+ 2 prefers to bind N over O donor sites, and decrease in N donor sites at the cavity prompts UO 2+ 2 to have better interaction with the rest of N donor centers. Extended transition state (ETS)with natural orbital for chemical valences (NOCV) analysis shows that at equatorial plane N acts as better σ donor to uranyl than O donor. Molecular orbital (MO) and density of states (DOS) analysis shows favorable bonding-interaction between U(d) and donor's p orbitals, the participation of U(f)-orbitals in bonding are of low-extent but non-negligible. Energy decomposition analysis (EDA), natural population analysis (NPA) along with thermodynamic analyses confirms the dominance of electrostatic interaction on the thermodynamic stability of the complexes. However, the U-N/O bonds at the equatorial plane do carry appreciable amount of covalent character. Analysis of quantum theory of atoms in molecules (QTAIM) descriptors in conjugation with MO analysis and overlap integral calculations confirms its nature as near-degeneracy driven type. Statistics of mixed-orbitals and overlap integral fur-

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Porphyrinoid f-Element Complexes

Cited by 29 publications

References 195 publications

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

Role of O Substitution in Expanded Porphyrins on Uranyl Complexation: Orbital- and Density-Based Analyses

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