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Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties
The substitution of three water molecules around trivalent chromium in CrBr(3)·6H(2)O with the tridentate 2,2′:6′,2′′-terpyridine (tpy), N,N′-dimethyl-N,N′-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br(3)] complexes. S...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8922558/ https://www.ncbi.nlm.nih.gov/pubmed/35195140 http://dx.doi.org/10.1039/d2dt00126h |
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author | Chong, Julien Besnard, Céline Cruz, Carlos M. Piguet, Claude Jiménez, Juan-Ramón |
author_facet | Chong, Julien Besnard, Céline Cruz, Carlos M. Piguet, Claude Jiménez, Juan-Ramón |
author_sort | Chong, Julien |
collection | PubMed |
description | The substitution of three water molecules around trivalent chromium in CrBr(3)·6H(2)O with the tridentate 2,2′:6′,2′′-terpyridine (tpy), N,N′-dimethyl-N,N′-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br(3)] complexes. Stepwise treatments with Ag(CF(3)SO(3)) and KCN under microwave irradiations provide mer-[Cr(L)(CN)(3)] in moderate yields. According to their X-ray crystal structures, the associated six-coordinate meridional [CrN(3)C(3)] chromophores increasingly deviate from a pseudo-octahedral arrangement according to L = ddpd ≈ dpq ≪ tpy; a trend in line with the replacement of six-membered with five-membered chelate rings around Cr(III). Room-temperature ligand-centered UV-excitation at 18 170 cm(−1) (λ(exc) = 350 nm), followed by energy transfer and intersystem crossing eventually yield microsecond metal-centered Cr((2)E → (4)A(2)) phosphorescence in the red to near infrared domain 13 150–12 650 cm(−1) (760 ≤ λ(em) ≤ 790 nm). Decreasing the temperature to liquid nitrogen (77 K) extends the emission lifetimes to reach the millisecond regime with a record of 4.02 ms for mer-[Cr(dqp)(CN)(3)] in frozen acetonitrile. |
format | Online Article Text |
id | pubmed-8922558 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-89225582022-04-06 Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties Chong, Julien Besnard, Céline Cruz, Carlos M. Piguet, Claude Jiménez, Juan-Ramón Dalton Trans Chemistry The substitution of three water molecules around trivalent chromium in CrBr(3)·6H(2)O with the tridentate 2,2′:6′,2′′-terpyridine (tpy), N,N′-dimethyl-N,N′-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br(3)] complexes. Stepwise treatments with Ag(CF(3)SO(3)) and KCN under microwave irradiations provide mer-[Cr(L)(CN)(3)] in moderate yields. According to their X-ray crystal structures, the associated six-coordinate meridional [CrN(3)C(3)] chromophores increasingly deviate from a pseudo-octahedral arrangement according to L = ddpd ≈ dpq ≪ tpy; a trend in line with the replacement of six-membered with five-membered chelate rings around Cr(III). Room-temperature ligand-centered UV-excitation at 18 170 cm(−1) (λ(exc) = 350 nm), followed by energy transfer and intersystem crossing eventually yield microsecond metal-centered Cr((2)E → (4)A(2)) phosphorescence in the red to near infrared domain 13 150–12 650 cm(−1) (760 ≤ λ(em) ≤ 790 nm). Decreasing the temperature to liquid nitrogen (77 K) extends the emission lifetimes to reach the millisecond regime with a record of 4.02 ms for mer-[Cr(dqp)(CN)(3)] in frozen acetonitrile. The Royal Society of Chemistry 2022-02-17 /pmc/articles/PMC8922558/ /pubmed/35195140 http://dx.doi.org/10.1039/d2dt00126h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Chong, Julien Besnard, Céline Cruz, Carlos M. Piguet, Claude Jiménez, Juan-Ramón Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title | Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title_full | Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title_fullStr | Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title_full_unstemmed | Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title_short | Heteroleptic mer-[Cr(N(∩)N(∩)N)(CN)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
title_sort | heteroleptic mer-[cr(n(∩)n(∩)n)(cn)(3)] complexes: synthetic challenge, structural characterization and photophysical properties |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8922558/ https://www.ncbi.nlm.nih.gov/pubmed/35195140 http://dx.doi.org/10.1039/d2dt00126h |
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