Pyridyl-benzimidazole derivatives decorated with phenylazo substituents and their low-spin iron( II ) complexes: a study of the synthesis, structure and photoisomerization

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F23%3APU147890" target="_blank" >RIV/00216305:26620/23:PU147890 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15310/23:73621962

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2023/NJ/D2NJ04774H" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2023/NJ/D2NJ04774H</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D2NJ04774H" target="_blank" >10.1039/D2NJ04774H</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Pyridyl-benzimidazole derivatives decorated with phenylazo substituents and their low-spin iron( II ) complexes: a study of the synthesis, structure and photoisomerization

Popis výsledku v původním jazyce

A series of phenylazo-substituted derivatives of pyridyl-benzimidazoles L1–L5 has been synthesized via a modified Mills reaction and their structural, spectral and photoswitching properties were investigated. NMR spectroscopy and single-crystal X-ray diffraction analysis of the desired compounds confirmed their E conformation. The light-induced E 2 Z (also called trans 2 cis) isomerization was monitored using UV-VIS and 1 H NMR spectroscopy that revealed a reversible photochromic behavior governed by first-order kinetics. State-of-the-art meta-dynamics simulations (iMTD-GC) and ab initio calculations (CASSCF-NEVPT2 and STEOM-DLPNO-CCSD) made the analysis of the electronic structures of ligands possible, which helped to explain the bland E-to-Z conversion of L1 and pronounced switching of L2– L5 ligands. Furthermore, the computational studies identified the active wavelengths of E-to-Z conversion and allowed assessing the mechanisms of photoisomerization. Additionally, ligands L1 and L2 were used for the preparation of four ferrous coordination compounds C1–C4 in which the structural and magnetic investigations confirmed the permanent low-spin state and diamagnetic behavior in the solid state. On the other hand, dissolved compounds C1 and C2 are high-spin at room temperature and their blue light irradiation causes the decomplexation instead of the desired E-to-Z isomerization.

Název v anglickém jazyce

Pyridyl-benzimidazole derivatives decorated with phenylazo substituents and their low-spin iron( II ) complexes: a study of the synthesis, structure and photoisomerization

Popis výsledku anglicky

A series of phenylazo-substituted derivatives of pyridyl-benzimidazoles L1–L5 has been synthesized via a modified Mills reaction and their structural, spectral and photoswitching properties were investigated. NMR spectroscopy and single-crystal X-ray diffraction analysis of the desired compounds confirmed their E conformation. The light-induced E 2 Z (also called trans 2 cis) isomerization was monitored using UV-VIS and 1 H NMR spectroscopy that revealed a reversible photochromic behavior governed by first-order kinetics. State-of-the-art meta-dynamics simulations (iMTD-GC) and ab initio calculations (CASSCF-NEVPT2 and STEOM-DLPNO-CCSD) made the analysis of the electronic structures of ligands possible, which helped to explain the bland E-to-Z conversion of L1 and pronounced switching of L2– L5 ligands. Furthermore, the computational studies identified the active wavelengths of E-to-Z conversion and allowed assessing the mechanisms of photoisomerization. Additionally, ligands L1 and L2 were used for the preparation of four ferrous coordination compounds C1–C4 in which the structural and magnetic investigations confirmed the permanent low-spin state and diamagnetic behavior in the solid state. On the other hand, dissolved compounds C1 and C2 are high-spin at room temperature and their blue light irradiation causes the decomplexation instead of the desired E-to-Z isomerization.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA22-23760S" target="_blank" >GA22-23760S: Sublimovatelné jednomolekulárni magnety pro přípravu nanostrukturních tenkých filmů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2023

Kód důvěrnosti údajů

C - Předmět řešení projektu podléhá obchodnímu tajemství (§ 504 Občanského zákoníku), ale název projektu, cíle projektu a u ukončeného nebo zastaveného projektu zhodnocení výsledku řešení projektu (údaje P03, P04, P15, P19, P29, PN8) dodané do CEP, jsou upraveny tak, aby byly zveřejnitelné.

Název periodika

NEW JOURNAL OF CHEMISTRY

ISSN

1144-0546

e-ISSN

1369-9261

Svazek periodika

47

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

1488-1497

Kód UT WoS článku

000901500700001

EID výsledku v databázi Scopus

2-s2.0-85144759080