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Inorganics
Special Issues
Metal Complexes as Nonlinear Optical Molecular Materials
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Metal Complexes as Nonlinear Optical Molecular Materials

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 October 2018) | Viewed by 26558

Special Issue Editors

Prof. Dr. Dominique Roberto

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Guest Editor
Dipartimento di Chimica, Università degli Studi di Milano, Via Venezian, 21, I-20133 Milano, Italy
Interests: coordination compounds; organometallic complexes; second-order nonlinear optics; second harmonic generation; dye-sensitized solar cells; luminescence
Dr. Alessia Colombo

E-Mail Website
Guest Editor
Department of Chemistry, University of Milan, Milan, Italy
Interests: synthesis; coordination chemistry; organic chemistry; solar cells; dyes; electrolites; luminescent complexes; OLEDs; nonlinear optics; bio-imaging; photodynamic therapy
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Claudia Dragonetti

E-Mail Website
Guest Editor
Department of Chemistry, University of Milan, Milan, Italy
Interests: coordination complexes; luminescent compounds; nonlinear optical materials; DSSCs
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Coordination and organometallic complexes with second- or third- order nonlinear optical (NLO) properties have attracted increasing attention as molecular building block materials for optical communications, optical data processing and storage or electro-optical devices. Remarkably, they present additional flexibility, when compared to organic chromophores, due to metal-ligand charge-transfer (MLCT) transitions, often at relatively low energy and of high intensity, tunable by choosing the nature, oxidation state, and coordination sphere of the metal center. In particular, metal complexes with commutable NLO responses are of interest for novel optoelectronic applications such as molecular-scale memory devices. This Special Issue aims at collecting research and review contributions of recent advances in all aspects of metal complexes with NLO properties and sharing given extensive knowledge with a broader audience by means of an open access way. This NLO issue is dedicated to Prof. Renato Ugo in occasion of his 80th birthday. We invite you to contribute papers in this fascinating research area and allow your work to impact the next generation NLO trend.

Prof. Dr. Dominique Roberto
Prof. Dr. Alessia Colombo
Prof. Dr. Claudia Dragonetti
Guest Editors

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. Inorganics is an international peer-reviewed open access monthly 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

  • Coordination compounds
  • Organometallic complexes
  • Second-order nonlinear optics
  • Second harmonic generation
  • Third-order nonlinear optics

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Published Papers (6 papers)

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Research

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12 pages, 2194 KiB  
Article
Impact of the Subunit Arrangement on the Nonlinear Absorption Properties of Organometallic Complexes with Ruthenium(II) σ-Acetylide and Benzothiadiazole as Building Units §
by Eleonora Garoni, Alessia Colombo, Kenji Kamada, Claudia Dragonetti and Dominique Roberto
Inorganics 2019, 7(5), 67; https://doi.org/10.3390/inorganics7050067 - 24 May 2019
Cited by 3 | Viewed by 2969
Abstract
In this paper, the nonlinear absorption properties of two complexes consisting of Ru(C≡CPh)(C≡C)(dppe)2 (dppe = Ph2PCH2CH2PPh2) as electron donor (D) and 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole as electron acceptor (A) units in two different arrangement, i.e., A–D–A and [...] Read more.
In this paper, the nonlinear absorption properties of two complexes consisting of Ru(C≡CPh)(C≡C)(dppe)2 (dppe = Ph2PCH2CH2PPh2) as electron donor (D) and 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole as electron acceptor (A) units in two different arrangement, i.e., A–D–A and D–A–D, are presented. They were measured in solution by the femtosecond open-aperture Z-scan method. The complexes show moderate two-photon absorption cross-sections σ(2) of several hundred to one thousand GM (here 1 GM = 10−50 cm4 s molecule−1 photon−1). Although they are formed by the same building units, it was found that the two-photon absorption values of the D–A–D arrangement are six times higher than that of the A–D–A one. This difference can be explained by the number of metal cores (one or two ruthenium centers), the geometrical configurations of the complexes (more or less planar), and the resonance enhancement by lowering the intermediate state. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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8 pages, 1904 KiB  
Article
The Role of Surface Plasmon Resonance of Gold Nanoparticles for the Enhancement of Second Harmonic Generation of Nonlinear Chromophores
by Anu Singh Bisht, Khuyen Hoang-Thi, Isabelle Ledoux-Rak, Hynd Remita, Frédéric Dumur, Audrey Guerlin, Eddy Dumas and Cédric R. Mayer
Inorganics 2019, 7(5), 64; https://doi.org/10.3390/inorganics7050064 - 18 May 2019
Cited by 1 | Viewed by 3091
Abstract
A significant enhancement of the second harmonic generation (SHG) from second-order nonlinear optical (NLO) dyes in solution has been evidenced when these dyes were grafted onto the surface of spherical gold nanoparticles (AuNPs), as compared to their NLO response without AuNPs. The length, [...] Read more.
A significant enhancement of the second harmonic generation (SHG) from second-order nonlinear optical (NLO) dyes in solution has been evidenced when these dyes were grafted onto the surface of spherical gold nanoparticles (AuNPs), as compared to their NLO response without AuNPs. The length, as well as the nature of the spacers between the gold particle and the chromophore, is shown to play an important role, a benzene linker being more favorable to AuNP-4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST) interactions, as illustrated by a higher exaltation of the NLO response for DAST molecules linked to AuNP via a phenyl ring as compared to their equivalent with a CH2–CH2 link. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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10 pages, 3917 KiB  
Article
Tuning the Linear and Nonlinear Optical Properties of Pyrene-Pyridine Chromophores by Protonation and Complexation to d10 Metal Centers §
by Elena Lucenti, Alessandra Forni, Daniele Marinotto, Andrea Previtali, Stefania Righetto and Elena Cariati
Inorganics 2019, 7(3), 38; https://doi.org/10.3390/inorganics7030038 - 9 Mar 2019
Cited by 10 | Viewed by 3399
Abstract
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) [...] Read more.
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) and Cu(I) to form the monomeric [Zn(CH3CO2)2(L1)2] complex and the [CuI(L2)]n coordination polymer, respectively. The structures of L1, L2, [Zn(CH3CO2)2(L1)2] and [CuI(L2)]n were determined by means of single-crystal X-ray diffraction studies. The NLO response, measured by the electric-field-induced second harmonic generation (EFISH) technique, was positive for both chromophores and showed an inversion of the sign after exposure to HCl vapors. This process was completely reversible and the original values were restored by simple exposure to NH3 vapors. Coordination of L1 to Zn(II) also resulted in a negative NLO response, although smaller in magnitude compared to the protonated form, due to the weak Lewis acidity of the “Zn(CH3CO2)2” fragment. The results were also interpreted on the basis of DFT/TDDFT calculations. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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Review

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18 pages, 4526 KiB  
Review
Zinc(II) as a Versatile Template for Efficient Dipolar and Octupolar Second-Order Nonlinear Optical Molecular Materials §
by Santo Di Bella, Alessia Colombo, Claudia Dragonetti, Stefania Righetto and Dominique Roberto
Inorganics 2018, 6(4), 133; https://doi.org/10.3390/inorganics6040133 - 11 Dec 2018
Cited by 32 | Viewed by 5691
Abstract
This short review outlines the main results obtained in the field of molecular materials based on zinc coordination compounds for second-order nonlinear optics. It presents an overview of the main classes of second-order nonlinear optical (NLO) active complexes bearing monodentate, bidentate, tridentate, or [...] Read more.
This short review outlines the main results obtained in the field of molecular materials based on zinc coordination compounds for second-order nonlinear optics. It presents an overview of the main classes of second-order nonlinear optical (NLO) active complexes bearing monodentate, bidentate, tridentate, or tetradentate π-delocalized ligands such as substituted stilbazoles, bipyridines, phenanthrolines, terpyridines, and Schiff bases. Macrocyclic ligands such as porphyrins and phthalocyanines are not covered. This paper shows how coordination to the Zn(II) center of π-delocalized nitrogen donor ligands produces a significant enhancement of their quadratic hyperpolarizability. Dipolar complexes are mainly presented, but octupolar zinc complexes are also presented. The coverage is mainly focused on NLO properties that are measured at the molecular level, working in solution, by means of the electric field-induced second harmonic generation (EFISH) or the hyper-Rayleigh scattering (HRS) techniques. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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38 pages, 24846 KiB  
Review
State of the Art of Boron and Tin Complexes in Second- and Third-Order Nonlinear Optics §
by Cristina C. Jiménez, Alejandro Enríquez-Cabrera, Oscar González-Antonio, Javier Ordóñez-Hernández, Pascal G. Lacroix, Pablo Labra-Vázquez, Norberto Farfán and Rosa Santillan
Inorganics 2018, 6(4), 131; https://doi.org/10.3390/inorganics6040131 - 10 Dec 2018
Cited by 17 | Viewed by 5833
Abstract
Boron and tin complexes have been a versatile and very interesting scaffold for the design of nonlinear optical (NLO) chromophores. In this paper we present a wide range of reports since the 1990s to date, which include second-order (e.g., second harmonic generation) and [...] Read more.
Boron and tin complexes have been a versatile and very interesting scaffold for the design of nonlinear optical (NLO) chromophores. In this paper we present a wide range of reports since the 1990s to date, which include second-order (e.g., second harmonic generation) and third-order (e.g., two-photon absorption) NLO properties. After a short introduction on the origin of the NLO response in molecules, the different features associated with the introduction of these inorganic motifs in the organic-based NLO materials are discussed: Their effect on the accepting/donating capabilities of the substituents, on the efficiency of the π-conjugated linkage, and on the topology of the chromophores which can be tuned from the first generation of “push-pull” chromophores to more sophisticated two- or three-dimensional architectures. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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17 pages, 1724 KiB  
Review
Porphyrins for Second Order Nonlinear Optics (NLO): An Intriguing History §
by Francesca Tessore, Alessio Orbelli Biroli, Gabriele Di Carlo and Maddalena Pizzotti
Inorganics 2018, 6(3), 81; https://doi.org/10.3390/inorganics6030081 - 20 Aug 2018
Cited by 37 | Viewed by 4749
Abstract
This short review outlines the main results obtained by our research group over the last 15 years in the field of porphyrins and metal porphyrins for second order nonlinear optics (NLO). This overview aims to provide a general framework of the key factors [...] Read more.
This short review outlines the main results obtained by our research group over the last 15 years in the field of porphyrins and metal porphyrins for second order nonlinear optics (NLO). This overview aims to provide a general framework of the key factors which affect the second order NLO response of porphyrin chromophores. The pivotal role of the porphyrin ring as π-conjugated linker, the nature of the metal center, the substitution pattern which features the geometrical arrangement of donor and acceptor substituents in the different classes of porphyrin NLO-phores, as well as the aggregation phenomena and the role of solvents are addressed in detail. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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