Effect of the Appended Morpholinyl Group on Photophysical Behavior of Mono- and Bis-cyclometalated Terpyridine Iridium(III) Chromophores DOI
Joanna Palion‐Gazda,

Aleksandra Kwiecień,

Katarzyna Choroba

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 646 - 661

Published: Dec. 26, 2024

This paper provides extensive studies of [IrCl(Ph-py)(morph-C6H4-terpy-κ3N)]PF6 (1A), [Ir(Ph-py)2(morph-C6H4-terpy-κ2N)]PF6 (2A), [IrCl(Ph-py)(Ph-terpy-κ3N)]PF6 (1B), and [Ir(Ph-py)2(Ph-terpy-κ2N)]PF6 (2B) designed to demonstrate the possibility controlling photophysical properties mono- bis-cyclometalated complexes [IrCl(Ph-py)(R-C6H4-terpy-κ3N)]PF6 [Ir(Ph-py)2(R-C6H4-terpy-κ2N)]PF6 through a remote electron-donating substituent introduced into 4′-position 2,2′:6′,2″-terpyridine (terpy) via phenyl linker. The attachment morpholinyl (morph) group was evidenced induce dramatic changes in emission characteristics monocyclometalated Ir(III) systems with meridionally coordinated R-C6H4-terpy ligand (κ3N). In solution, obtained complex found be rare example dual-emissive systems. Within series bearing bound central ion bidentate coordination mode, appended induced minor effect on maximum, but it an effective tool for extending excited-state lifetime, further prolonging increase solvent polarity. results this work are high significance better understanding push–pull dual-emission phenomena Ir-based luminophores, as well developing chromophores prolonged lifetimes.

Language: Английский

Anticancer profile of coumarin 6-based Ir(iii) photocatalysts under normoxia and hypoxia by ROS generation and NADH oxidation DOI
Ashish Kumar Yadav, Aarti Upadhyay, Arpan Bera

et al.

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 5435 - 5448

Published: Jan. 1, 2024

Coumarin 6 appended Ir( iii ) photocatalysts exhibited light activated anticancer effects against cancer cells via mitochondrial depolarization driven apoptosis by inducing type-I (NADH oxidation) and type-II (ROS generation) mechanisms.

Language: Английский

Citations

11
Intracellular Photocatalytic NADH/NAD(P)H Oxidation for Cancer Drug Development DOI
Ashish Yadav, Samya Banerjee,

Arif Ali Mandal

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7161 - 7181

Published: Feb. 20, 2025

Photocatalytic cancer therapy (PCT) has emerged as a cutting-edge anticancer mechanism of action, harnessing light energy to mediate the catalytic oxidation intracellular substrates. PCT is significant current importance due its potential address limitations conventional chemotherapy, particularly drug resistance and side effects. This approach offers noninvasive, targeted treatment option by utilizing metal-based photocatalysts induce redox metabolic disorders within cells. The disrupt cell metabolism converting NADH/NAD(P)H NAD+/NAD(P)+ via photoredox processes, altering NAD+/NADH or NAD(P)+/NAD(P)H ratios, which are crucial for cellular metabolism. Ir(III), Ru(II), Re(I), Os(II) demonstrated promising efficacy. Despite these developments, gaps remain in literature translating this new into clinical trials. Perspective critically examines developments research area provides future directions designing efficient PCT.

Language: Английский

Citations

1
RuIII–Morpholine-Derived Thiosemicarbazone-Based Metallodrugs: Lysosome-Targeted Anticancer Agents DOI
Monalisa Mohanty, Sanchita Das,

Pratikshya Das Pattanayak

et al.

ACS Applied Bio Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

The idea of coordinating biologically active ligand systems to metal centers exploit their synergistic effects has gained momentum. Therefore, in this report, three RuIII complexes 1–3 morpholine-derived thiosemicarbazone ligands have been prepared and characterized by spectroscopy HRMS along with the structure 2 through a single-crystal X-ray diffraction study. solution stability was tested using conventional techniques such as UV–vis HRMS. Further, anticancer activity HT-29 HeLa cancer cell lines. To gain insight into mechanism action, cytotoxicity, hydrophobicity, interaction DNA HSA were evaluated different methods absorption, fluorescence, circular dichroism studies. Along favorable biomolecule interaction, revealed potent selectivity toward cells, which is prerequisite for generation an drug. According viability results, 1 highest cytotoxicity among all group, against both respectively. Additionally, fluorescence-active ruthenium selectively target lysosomes, live-cell imaging. disrupt lysosome membrane potential generating excessive amount reactive oxygen species, results apoptotic mode death.

Language: Английский

Citations

0
Anticancer potential of polypyridyl-based Ir(III)-coumarin 6 conjugates under visible light and dark DOI
Ashish Kumar Yadav, Virendra Singh, Samya Banerjee

et al.

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 114184 - 114184

Published: Feb. 1, 2025

Language: Английский

Citations

0
Metalla-Aromatic Oligomers: Efficient Photocatalytic Activation for Phototherapy DOI
Shiyan Chen, Guotao Yuan, Liu Wang

et al.

Journal of Medicinal Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 1, 2025

Monodisperse oligomers, positioned as intermediates between polymers and small molecules, retain certain reactivities of molecules while simultaneously displaying the initial aggregation characteristics polymers. This distinctive structure bestows on them with significant potential for a wide range applications. In this study, series carbolong osmium oligomers (Os1-Os4) corresponding polymer were evaluated photocatalysts. It was discovered that their molar absorption coefficients reactive oxygen species generation rose π-conjugation length, peaking at polymerization degree 4. Moreover, Os4 facilitates photocatalytic oxidation nicotinamide adenine dinucleotide (NADH) to its oxided form, NAD+. vitro experiments demonstrated had strongest phototoxicity index in cells hypoxic conditions, highlighting efficacy tumor. Metabolomic analyses indicated exerted photocytotoxicity by disrupting purine metabolism. These insights will guide future design π-conjugated metal advancing

Language: Английский

Citations

0
The Role of Intraligand Charge Transfer Processes in Iridium(III) Complexes with Morpholine-Decorated 4′-Phenyl-2,2′:6′,2″-terpyridine DOI Creative Commons
Joanna Palion‐Gazda,

Aleksandra Kwiecień,

Katarzyna Choroba

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(13), P. 3074 - 3074

Published: June 27, 2024

To investigate the impact of electron-donating morpholinyl (morph) group on ground- and excited-state properties two different types Ir(III) complexes, [IrCl3(R-C6H4-terpy-κ3N)] [Ir(R-C6H4-terpy-κ3N)2](PF6)3, compounds [IrCl3(morph-C6H4-terpy-κ3N)] (1A), 4[Ir(morph-C6H4-terpy-κ3N)2](PF6)3 (2A), [IrCl3(Ph-terpy-κ3N)] (1B) [Ir(Ph-terpy-κ3N)2](PF6)3 (2B) were obtained. Their photophysical comprehensively investigated with aid static time-resolved spectroscopic methods accompanied by theoretical DFT/TD-DFT calculations. In case bis-terpyridyl iridium(III) attachment induced dramatic changes in absorption emission characteristics, manifested appearance a new, very strong visible tailing up to 600 nm, significant bathochromic shift 2A relative model chromophore. The features 2B found originate from triplet excited states natures: intraligand charge transfer (3ILCT) for small admixture metal-to-ligand (3IL–3MLCT) 2B. optical mono-terpyridyl complexes less significantly impacted substituent. Based UV–Vis spectra, wavelengths lifetimes environments, transient studies, calculations, it was demonstrated that 1A are governed singlet mixed MLLCT-ILCT nature, dominant contribution first component, is, metal-ligand-to-ligand (MLLCT). involvement ILCT transitions reflected an enhancement molar extinction coefficients bands range 350–550 red its

Language: Английский

Citations

2
Vitamin B6 appended polypyridyl Co(III) complexes for photo‐triggered antibacterial activity DOI
Samya Banerjee,

Apurba Mandal,

Rohit Rai

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

Abstract Three novel polypyridyl‐Co(III)‐vitamin B 6 complexes viz ., [Co(CF 3 ‐phtpy)(SBVB )]Cl ( Co1 ), [Co(anthracene‐tpy)(SBVB Co2 [Co(NMe 2 Co3 where 4’‐(4‐(trifluoromethyl)phenyl)‐2,2’:6’,2’’‐terpyridine=CF ‐phtpy, 4’‐(anthracen‐9‐yl)‐2,2’:6’,2’’‐terpyridine=anthracene‐tpy;, 4‐([2,2’:6’,2’’‐terpyridin]‐4’‐yl)‐N,N‐dimethylaniline=NMe (E)‐5‐(hydroxymethyl)‐4‐(((2‐hydroxyphenyl)imino)methyl)‐2‐methylpyridin‐3‐ol=H SBVB were successfully developed for aPDT (antibacterial photodynamic therapy) applications. – exhibited an intense absorption band at ca . 435–485 nm, which is attributed to ligand‐to‐metal charge transfer and was beneficial antibacterial therapy. The distorted octahedral geometry of the with Co III N 4 O core evident from DFT study. visible light ability good photo‐stability made them photosensitizers aPDT. displayed significant responses against gram‐positive S. aureus ) gram‐negative E. coli bacteria upon exposure (10 J cm −2 , 400–700 nm) showed MIC values between 0.01–0.005 μg mL −1 activities these due their damage bacterial cell membranes via ROS generation. Overall, this study shows photo‐triggered ROS‐mediated bacteria‐killing potential Co(III) complexes.

Language: Английский

Citations

2
Recent advances in Rh(III)-based anticancer complexes DOI
Souvik Saha, Rajesh Kushwaha,

Apurba Mandal

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 525, P. 216306 - 216306

Published: Nov. 22, 2024

Language: Английский

Citations

2
Aggregation‐Enhanced Photodynamic Activity of Organometallic Ru(II)–Arene Complexes DOI
Jingjing Bu, Zhiwei Xu, Yanyan Sun

et al.

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 39(1)

Published: Sept. 24, 2024

ABSTRACT Organometallic Ru(II)–arene complexes have emerged as potential chemotherapeutic agents for improved cancer treatment. However, the application of photosensitizers has been rarely explored. In consideration their excellent biological performance, herein, three 1–3 bearing 2,3,8,9,14,15‐hexamethyl‐5,6,11,12,17,18‐hexaazatrinapthalene (HATN‐Me 6 ) acceptor ligand designed and investigated photosensitizers. Distinctively, produced negligible singlet oxygen ( 1 O 2 generation in DMF. The mechanism investigations indicated that large change equilibrium displacement between excited ground states rather than narrow energy gap results increased vibrational wave function overlap non‐radiative decay rate. Remarkably, induced greatly enhanced efficiency an aggregated state due to suppression process, implying electronic structures play essential role photochemical properties functions organometallic complexes. evaluation showed exhibited potent photocytotoxicity against cells, highlighting scaffolds are platforms fabrication efficient

Language: Английский

Citations

0
Effect of the Appended Morpholinyl Group on Photophysical Behavior of Mono- and Bis-cyclometalated Terpyridine Iridium(III) Chromophores DOI
Joanna Palion‐Gazda,

Aleksandra Kwiecień,

Katarzyna Choroba

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 646 - 661

Published: Dec. 26, 2024

This paper provides extensive studies of [IrCl(Ph-py)(morph-C6H4-terpy-κ3N)]PF6 (1A), [Ir(Ph-py)2(morph-C6H4-terpy-κ2N)]PF6 (2A), [IrCl(Ph-py)(Ph-terpy-κ3N)]PF6 (1B), and [Ir(Ph-py)2(Ph-terpy-κ2N)]PF6 (2B) designed to demonstrate the possibility controlling photophysical properties mono- bis-cyclometalated complexes [IrCl(Ph-py)(R-C6H4-terpy-κ3N)]PF6 [Ir(Ph-py)2(R-C6H4-terpy-κ2N)]PF6 through a remote electron-donating substituent introduced into 4′-position 2,2′:6′,2″-terpyridine (terpy) via phenyl linker. The attachment morpholinyl (morph) group was evidenced induce dramatic changes in emission characteristics monocyclometalated Ir(III) systems with meridionally coordinated R-C6H4-terpy ligand (κ3N). In solution, obtained complex found be rare example dual-emissive systems. Within series bearing bound central ion bidentate coordination mode, appended induced minor effect on maximum, but it an effective tool for extending excited-state lifetime, further prolonging increase solvent polarity. results this work are high significance better understanding push–pull dual-emission phenomena Ir-based luminophores, as well developing chromophores prolonged lifetimes.

Language: Английский

Citations

0