A novel type of heteroleptic Cu(i) complexes featuring nitrogen-rich tetrazine ligands: syntheses, crystal structures, spectral properties, cyclic voltammetry, and theoretical calculations

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F25%3A73633967" target="_blank" >RIV/61989592:15310/25:73633967 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03137g" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03137g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt03137g" target="_blank" >10.1039/d4dt03137g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A novel type of heteroleptic Cu(i) complexes featuring nitrogen-rich tetrazine ligands: syntheses, crystal structures, spectral properties, cyclic voltammetry, and theoretical calculations

Popis výsledku v původním jazyce

Heteroleptic copper(i) complexes with the general formula [Cu(N&lt;^&gt;N)(P&lt;^&gt;P)]X constitute one of the most studied categories of 3d metal photosensitizers. Here, we examine using 1,2,4,5-tetrazine-based ligands to synthesize photoactive Cu(i) complexes. The newly prepared complexes were characterized by single-crystal X-ray analysis, which revealed the formation of dinuclear complexes [Cu2(mu-L1)(xantphos)2](ClO4)2 (1) and [Cu2(mu-L2)(xantphos)2](ClO4)2 (2), and mononuclear complexes [Cu(L3)(xantphos)]ClO4 (3) and [Cu(L4)(xantphos)]ClO4 (4), where L1 = 3,6-di(2 &apos;-pyridyl)-1,2,4,5-tetrazine (bptz), L2 = 3,6-bis-(3,5-dimethyl-pyrazol-1-yl)-1,2,4,5-tetrazine, L3 = 3-(2-pyridyl)-1,2,4,5-tetrazine, L4 = 3-(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine and xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. Solution stability assays were addressed by NMR spectroscopy showing that complexes are stable in dichloromethane over several days. The electronic excited states were investigated by UV-Vis and luminiscence spectroscopy and interpreted with the help of TD-DFT calculations. In the case of all the newly prepared complexes 1-4, the absorptions in the visible region were assigned to non-emissive MLCT transitions between the Cu(i) and the respective tetrazine ligand. Redox properties were probed by cyclic voltammetry and also supplemented by DFT calculations. Interestingly, tetrazine ligands L1-L4 show a shift of reduction potential to less negative values upon the formation of Cu(i) complexes 1-4. Moreover, the two complexes 3-4 represent the first reported case of mononuclear heteroleptic Cu(i)-tetrazine complexes.

Název v anglickém jazyce

A novel type of heteroleptic Cu(i) complexes featuring nitrogen-rich tetrazine ligands: syntheses, crystal structures, spectral properties, cyclic voltammetry, and theoretical calculations

Popis výsledku anglicky

Heteroleptic copper(i) complexes with the general formula [Cu(N&lt;^&gt;N)(P&lt;^&gt;P)]X constitute one of the most studied categories of 3d metal photosensitizers. Here, we examine using 1,2,4,5-tetrazine-based ligands to synthesize photoactive Cu(i) complexes. The newly prepared complexes were characterized by single-crystal X-ray analysis, which revealed the formation of dinuclear complexes [Cu2(mu-L1)(xantphos)2](ClO4)2 (1) and [Cu2(mu-L2)(xantphos)2](ClO4)2 (2), and mononuclear complexes [Cu(L3)(xantphos)]ClO4 (3) and [Cu(L4)(xantphos)]ClO4 (4), where L1 = 3,6-di(2 &apos;-pyridyl)-1,2,4,5-tetrazine (bptz), L2 = 3,6-bis-(3,5-dimethyl-pyrazol-1-yl)-1,2,4,5-tetrazine, L3 = 3-(2-pyridyl)-1,2,4,5-tetrazine, L4 = 3-(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine and xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. Solution stability assays were addressed by NMR spectroscopy showing that complexes are stable in dichloromethane over several days. The electronic excited states were investigated by UV-Vis and luminiscence spectroscopy and interpreted with the help of TD-DFT calculations. In the case of all the newly prepared complexes 1-4, the absorptions in the visible region were assigned to non-emissive MLCT transitions between the Cu(i) and the respective tetrazine ligand. Redox properties were probed by cyclic voltammetry and also supplemented by DFT calculations. Interestingly, tetrazine ligands L1-L4 show a shift of reduction potential to less negative values upon the formation of Cu(i) complexes 1-4. Moreover, the two complexes 3-4 represent the first reported case of mononuclear heteroleptic Cu(i)-tetrazine complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

54

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

5944-5952

Kód UT WoS článku

001445916800001

EID výsledku v databázi Scopus

2-s2.0-105002381345