Pentadentate and Hexadentate Pyridinophane Ligands Support Reversible Cu(II)/Cu(I) Redox Couples

Glenn Blade; Andrew J. Wessel; Karna Terpstra; Liviu M. Mirica

doi:10.3390/inorganics11110446

Pentadentate and Hexadentate Pyridinophane Ligands Support Reversible Cu(II)/Cu(I) Redox Couples

Glenn Blade, Andrew J. Wessel, Karna Terpstra, Liviu M. Mirica

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Two new ligands were synthesized with the goal of copper stabilization, N,N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (^PicN4) and N-(methyl),N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (^PicMeN4), by selective functionalization of ^HN4 and ^TsHN4. These two ligands, when reacted with various copper salts, generated both Cu(II) and Cu(I) complexes. These ligands and Cu complexes were characterized by various methods, such as NMR, UV-Vis, MS, and EA. Each compound was also examined electrochemically, and each revealed reversible Cu(II)/Cu(I) redox couples. Additionally, stability constants were determined via spectrophotometric titrations, and radiolabeling and cytotoxicity experiments were performed to assess the chelators relevance to their potential use in vivo as ⁶⁴Cu PET imaging agents.

Original language	English
Article number	446
Journal	Inorganics
Volume	11
Issue number	11
DOIs	https://doi.org/10.3390/inorganics11110446
State	Published - Nov 2023

Keywords

Cu PET imaging agents
bioinorganic chemistry
copper(I) complexes
copper(II) complexes
cyclic voltammetry
pyridinophane ligands
radiolabeling
reversibility

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@article{dd28e00320814691a8ec68a8afed0742,

title = "Pentadentate and Hexadentate Pyridinophane Ligands Support Reversible Cu(II)/Cu(I) Redox Couples",

abstract = "Two new ligands were synthesized with the goal of copper stabilization, N,N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicN4) and N-(methyl),N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicMeN4), by selective functionalization of HN4 and TsHN4. These two ligands, when reacted with various copper salts, generated both Cu(II) and Cu(I) complexes. These ligands and Cu complexes were characterized by various methods, such as NMR, UV-Vis, MS, and EA. Each compound was also examined electrochemically, and each revealed reversible Cu(II)/Cu(I) redox couples. Additionally, stability constants were determined via spectrophotometric titrations, and radiolabeling and cytotoxicity experiments were performed to assess the chelators relevance to their potential use in vivo as 64Cu PET imaging agents.",

keywords = "Cu PET imaging agents, bioinorganic chemistry, copper(I) complexes, copper(II) complexes, cyclic voltammetry, pyridinophane ligands, radiolabeling, reversibility",

author = "Glenn Blade and Wessel, {Andrew J.} and Karna Terpstra and Mirica, {Liviu M.}",

note = "Publisher Copyright: {\textcopyright} 2023 by the authors.",

year = "2023",

month = nov,

doi = "10.3390/inorganics11110446",

language = "English",

volume = "11",

journal = "Inorganics",

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T1 - Pentadentate and Hexadentate Pyridinophane Ligands Support Reversible Cu(II)/Cu(I) Redox Couples

AU - Blade, Glenn

AU - Wessel, Andrew J.

AU - Terpstra, Karna

AU - Mirica, Liviu M.

PY - 2023/11

Y1 - 2023/11

N2 - Two new ligands were synthesized with the goal of copper stabilization, N,N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicN4) and N-(methyl),N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicMeN4), by selective functionalization of HN4 and TsHN4. These two ligands, when reacted with various copper salts, generated both Cu(II) and Cu(I) complexes. These ligands and Cu complexes were characterized by various methods, such as NMR, UV-Vis, MS, and EA. Each compound was also examined electrochemically, and each revealed reversible Cu(II)/Cu(I) redox couples. Additionally, stability constants were determined via spectrophotometric titrations, and radiolabeling and cytotoxicity experiments were performed to assess the chelators relevance to their potential use in vivo as 64Cu PET imaging agents.

AB - Two new ligands were synthesized with the goal of copper stabilization, N,N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicN4) and N-(methyl),N′-(2-methylpyridine)-2,11-diaza[3,3](2,6)pyridinophane (PicMeN4), by selective functionalization of HN4 and TsHN4. These two ligands, when reacted with various copper salts, generated both Cu(II) and Cu(I) complexes. These ligands and Cu complexes were characterized by various methods, such as NMR, UV-Vis, MS, and EA. Each compound was also examined electrochemically, and each revealed reversible Cu(II)/Cu(I) redox couples. Additionally, stability constants were determined via spectrophotometric titrations, and radiolabeling and cytotoxicity experiments were performed to assess the chelators relevance to their potential use in vivo as 64Cu PET imaging agents.

KW - Cu PET imaging agents

KW - bioinorganic chemistry

KW - copper(I) complexes

KW - copper(II) complexes

KW - cyclic voltammetry

KW - pyridinophane ligands

KW - radiolabeling

KW - reversibility

UR - http://www.scopus.com/inward/record.url?scp=85178294835&partnerID=8YFLogxK

U2 - 10.3390/inorganics11110446

DO - 10.3390/inorganics11110446

M3 - Article

C2 - 39301085

AN - SCOPUS:85178294835

SN - 2304-6740

VL - 11

JO - Inorganics

JF - Inorganics

IS - 11

M1 - 446

ER -

Pentadentate and Hexadentate Pyridinophane Ligands Support Reversible Cu(II)/Cu(I) Redox Couples

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Keywords

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