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Molecules
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Photochemical Studies of Metal Complexes
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Photochemical Studies of Metal Complexes

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Photochemistry".

Deadline for manuscript submissions: closed (31 January 2024) | Viewed by 3941

Special Issue Editor

Prof. Dr. Conor Long

E-Mail Website
Guest Editor
School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
Interests: organometallic photochemistry; quantum chemistry; organometallic synthesis; matrix isolation; time-resolved spectroscopy; chemical kinetics

Special Issue Information

Dear Colleagues,

The photochemistry of metal complexes is a diverse research domain ranging from fundamental quantum chemical calculations to practical applications in therapeutic medicine and device manufacturing. A broad range of techniques are used in these studies from ultrafast lasers to slow cryogenic methods which use a wide range of spectroscopic and spectrometric methods. These studies have revealed many useful processes from ligand transformations to catalysis, small-molecule activation, singlet oxygen generation, and DNA scission, to mention just a few. Metal complexes are also used as photo-switches and in the design of novel solar cells, and have found uses in photodynamic therapy and in the design of mechanoresponsive materials and materials with antimicrobial activity. Therefore, this research domain is broad in scope and rich in practical applications.

I would like to invite you to submit original research papers or review articles to this Special Issue that would address any research topic related to the photochemistry of metal complexes.

Prof. Dr. Conor Long
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • catalysis
  • electronic structure
  • excited state dynamics
  • small-molecule activation
  • materials
  • DNA
  • photodynamic therapy
  • synthesis

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Published Papers (2 papers)

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Research

20 pages, 6455 KiB  
Article
The Role of Intraligand Charge Transfer Processes in Iridium(III) Complexes with Morpholine-Decorated 4′-Phenyl-2,2′:6′,2″-terpyridine
by Joanna Palion-Gazda, Aleksandra Kwiecień, Katarzyna Choroba, Mateusz Penkala, Anna Kryczka and Barbara Machura
Molecules 2024, 29(13), 3074; https://doi.org/10.3390/molecules29133074 - 27 Jun 2024
Cited by 3 | Viewed by 1175
Abstract
To investigate the impact of the electron-donating morpholinyl (morph) group on the ground- and excited-state properties of two different types of Ir(III) complexes, [IrCl3(R-C6H4-terpy-κ3N)] and [Ir(R-C6H4-terpy-κ3N)2](PF6 [...] Read more.
To investigate the impact of the electron-donating morpholinyl (morph) group on the ground- and excited-state properties of two different types of Ir(III) complexes, [IrCl3(R-C6H4-terpy-κ3N)] and [Ir(R-C6H4-terpy-κ3N)2](PF6)3, the compounds [IrCl3(morph-C6H4-terpy-κ3N)] (1A), 4[Ir(morph-C6H4-terpy-κ3N)2](PF6)3 (2A), [IrCl3(Ph-terpy-κ3N)] (1B) and [Ir(Ph-terpy-κ3N)2](PF6)3 (2B) were obtained. Their photophysical properties were comprehensively investigated with the aid of static and time-resolved spectroscopic methods accompanied by theoretical DFT/TD-DFT calculations. In the case of bis-terpyridyl iridium(III) complexes, the attachment of the morpholinyl group induced dramatic changes in the absorption and emission characteristics, manifested by the appearance of a new, very strong visible absorption tailing up to 600 nm, and a significant bathochromic shift in the emission of 2A relative to the model chromophore. The emission features of 2A and 2B were found to originate from the triplet excited states of different natures: intraligand charge transfer (3ILCT) for 2A and intraligand with a small admixture of metal-to-ligand charge transfer (3IL–3MLCT) for 2B. The optical properties of the mono-terpyridyl iridium(III) complexes were less significantly impacted by the morpholinyl substituent. Based on UV–Vis absorption spectra, emission wavelengths and lifetimes in different environments, transient absorption studies, and theoretical calculations, it was demonstrated that the visible absorption and emission features of 1A are governed by singlet and triplet excited states of a mixed MLLCT-ILCT nature, with a dominant contribution of the first component, that is, metal-ligand-to-ligand charge transfer (MLLCT). The involvement of ILCT transitions was reflected by an enhancement of the molar extinction coefficients of the absorption bands of 1A in the range of 350–550 nm, and a small red shift in its emission relative to the model chromophore. Full article
(This article belongs to the Special Issue Photochemical Studies of Metal Complexes)
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20 pages, 2719 KiB  
Article
The Liquid Jet Endstation for Hard X-ray Scattering and Spectroscopy at the Linac Coherent Light Source
by Cali Antolini, Victor Sosa Alfaro, Marco Reinhard, Gourab Chatterjee, Ryan Ribson, Dimosthenis Sokaras, Leland Gee, Takahiro Sato, Patrick L. Kramer, Sumana Laxmi Raj, Brandon Hayes, Pamela Schleissner, Angel T. Garcia-Esparza, Jinkyu Lim, Jeffrey T. Babicz, Jr., Alec H. Follmer, Silke Nelson, Matthieu Chollet, Roberto Alonso-Mori and Tim B. van Driel
Molecules 2024, 29(10), 2323; https://doi.org/10.3390/molecules29102323 - 15 May 2024
Cited by 3 | Viewed by 2069
Abstract
The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires [...] Read more.
The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires specialized experimental endstations along with the development of techniques and methods to successfully carry out experiments. The liquid jet endstation (LJE) at the Linac Coherent Light Source (LCLS) has been developed to study photochemistry and biochemistry in solution systems using a combination of X-ray solution scattering (XSS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). The pump–probe setup utilizes an optical laser to excite the sample, which is subsequently probed by a hard X-ray pulse to resolve structural and electronic dynamics at their intrinsic femtosecond timescales. The LJE ensures reliable sample delivery to the X-ray interaction point via various liquid jets, enabling rapid replenishment of thin samples with millimolar concentrations and low sample volumes at the 120 Hz repetition rate of the LCLS beam. This paper provides a detailed description of the LJE design and of the techniques it enables, with an emphasis on the diagnostics required for real-time monitoring of the liquid jet and on the spatiotemporal overlap methods used to optimize the signal. Additionally, various scientific examples are discussed, highlighting the versatility of the LJE. Full article
(This article belongs to the Special Issue Photochemical Studies of Metal Complexes)
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