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Crystals
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Self-Assembled Complexes: “Love at First Sight”
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Self-Assembled Complexes: “Love at First Sight”

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (20 January 2023) | Viewed by 18258

Special Issue Editors

Dr. Ana M. Garcia-Deibe

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Guest Editor
Department of Inorganic Chemistry, Universidade de Santiago de Compostela, Campus Vida, E-15782 Santiago de Compostela, Spain
Interests: supramolecular chemistry; coordination chemistry; single crystal X-ray crystallography; H-bonding; chirality; fluorescence
Special Issues, Collections and Topics in MDPI journals
Dr. Jesús Sanmartín-Matalobos

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Guest Editor
Inorganic Chemistry Department, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
Interests: supramolecular chemistry; coordination chemistry; single crystal X-ray crystallography; H-bonding; chirality; fluorescence
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The development of many fields related to chemistry (materials, catalysts, pharmaceuticals, dyes, etc.) can have deep impacts on social progress. Many advances are closely related to the progress of coordination chemistry, since the combination of metal atoms with diverse ligands can result in a wide range of physicochemical properties, some of which are novel, which we can take advantage of in different areas. While many improvements have resulted from serendipity and many others from a designed plan, self-assembly is usually involved in coordination processes. The spontaneity of processes to form not only small single ion molecules but also intricate frameworks, such as MOFs, is difficult to understand as this spontaneity appears to be “love at first sight”. However, it is crucial to precisely structure materials at a nanometric scale, which is a current goal of materials science as well.

In order to provide an opportunity to disseminate knowledge in this crucial field of chemistry, we invite contributions with a research focus on metal complexes and related materials, as well as those exploring their features or potential applications.

While examples of possible topics are listed in the keywords, this Special Issue is open to any advanced topic in the field.

Dr. Ana Garcia-Deibe
Prof. Dr. Jesús Sanmartín-Matalobos
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. Crystals 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 2100 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

  • synthesis and characterization of self-assembled complexes
  • complex stability and bonding properties
  • metal complexes in bioinorganic chemistry
  • coordination polymers
  • metallorganic materials
  • MOFs
  • metal complexes in catalysis
  • analytical applications of metal complexes
  • crystal engineering in coordination chemistry
  • molecular design and structure prediction
  • coordination geometry
  • novel coordination modes
  • chirality in metal complexes
  • isomerism in metal complexes

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Published Papers (7 papers)

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Editorial

Jump to: Research, Review

4 pages, 220 KiB  
Editorial
Self–Assembled Complexes: “Love at First Sight”
by Ana M. García-Deibe and Jesús Sanmartín-Matalobos
Crystals 2024, 14(6), 544; https://doi.org/10.3390/cryst14060544 - 11 Jun 2024
Viewed by 907
Abstract
Self-assembly is a key process to obtain auto-organized species from disordered components [...] Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)

Research

Jump to: Editorial, Review

14 pages, 8552 KiB  
Article
Monte Carlo Simulations of the Metal-Directed Self-Assembly of Y-Shaped Positional Isomers
by Karolina Nieckarz and Damian Nieckarz
Crystals 2022, 12(4), 492; https://doi.org/10.3390/cryst12040492 - 1 Apr 2022
Cited by 8 | Viewed by 2038
Abstract
The rational fabrication of low-dimensional materials with a well-defined topology and functions is an incredibly important aspect of nanotechnology. In particular, the on-surface synthesis (OSS) methods based on the bottom-up approach enable a facile construction of sophisticated molecular architectures unattainable by traditional methods [...] Read more.
The rational fabrication of low-dimensional materials with a well-defined topology and functions is an incredibly important aspect of nanotechnology. In particular, the on-surface synthesis (OSS) methods based on the bottom-up approach enable a facile construction of sophisticated molecular architectures unattainable by traditional methods of wet chemistry. Among such supramolecular constructs, especially interesting are the surface-supported metal–organic networks (SMONs), composed of low-coordinated metal atoms and π-aromatic bridging linkers. In this work, the lattice Monte Carlo (MC) simulation technique was used to extract the chemical information encoded in a family of Y-shaped positional isomers co-adsorbed with trivalent metal atoms on a flat metallic surface with (111) geometry. Depending on the intramolecular distribution of active centers (within the simulated molecular bricks, we observed a metal-directed self-assembly of two-dimensional (2D) openwork patterns, aperiodic mosaics, and metal–organic ladders. The obtained theoretical findings could be especially relevant for the scanning tunneling microscopy (STM) experimentalists interested in a surface-assisted construction of complex nanomaterials stabilized by directional coordination bonds. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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10 pages, 4411 KiB  
Article
Molecular Self-Assembly of an Unusual Dinuclear Ruthenium(III) Complex Based on the Nucleobase Guanine
by Marta Orts-Arroyo, Adriana Silvestre-Llora, Isabel Castro and José Martínez-Lillo
Crystals 2022, 12(4), 448; https://doi.org/10.3390/cryst12040448 - 23 Mar 2022
Cited by 4 | Viewed by 2377
Abstract
The study of crystal structures based on complexes containing purine nucleobases is a significant research subject, mainly regarding the diagnosis and treatment of some diseases and the investigation of genetic mutations and biochemical structures in life sciences. We have obtained and characterized a [...] Read more.
The study of crystal structures based on complexes containing purine nucleobases is a significant research subject, mainly regarding the diagnosis and treatment of some diseases and the investigation of genetic mutations and biochemical structures in life sciences. We have obtained and characterized a new dinuclear ruthenium(III) complex based on guanine with the formula [{Ru(µ-Cl)(µ-gua)}2Cl4]·2H2O (1) (gua = guanine). 1 was characterized by means of Fourier transform infrared spectroscopy (FT–IR), scanning electron microscopy and energy dispersive X-ray analysis (SEM–EDX), single-crystal X-ray diffraction (XRD), Hirshfeld surface analysis and cyclic voltammetry (CV). The study of its electrochemical properties allowed us to investigate the presence of guanine molecules when linked to the ruthenium(III) ion in 1. The well-resolved voltammetric response together with the reliability and stability achieved through 1 could provide a step forward to developing new ruthenium-based platforms, devices and modified electrodes adequate to study this purine nucleobase. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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Figure 1

7 pages, 1826 KiB  
Article
[Tb4(OH)4]-Cuboid Complex Dianion Stabilized with Six Carboxylate Bridges and Four Diketonate Caps
by Yoshiki Yamaguchi and Takayuki Ishida
Crystals 2022, 12(3), 402; https://doi.org/10.3390/cryst12030402 - 16 Mar 2022
Cited by 2 | Viewed by 1795
Abstract
A cubane-like complex dianion [Tb4(OH)4(tfa)6(hfac)4]2− was synthesized, accompanied by two counter cations of [Ni(hfac)(2pyIN)2]+, where Htfa, Hhfac, and 2pyIN stand for trifluoroacetic acid, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, and 4,4,5,5-tetramethyl-2-pyridylimidazolin-1-oxyl, respectively. In the complex [...] Read more.
A cubane-like complex dianion [Tb4(OH)4(tfa)6(hfac)4]2− was synthesized, accompanied by two counter cations of [Ni(hfac)(2pyIN)2]+, where Htfa, Hhfac, and 2pyIN stand for trifluoroacetic acid, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, and 4,4,5,5-tetramethyl-2-pyridylimidazolin-1-oxyl, respectively. In the complex anion, each Tb ion was capped with hfac, and each Tb···Tb diagonal was bridged with tfa, thus forming an approximate Td symmetry, though the whole molecular formula was crystallographically independent in an orthorhombic Pbca space group. The ionic charge was −2 in total. The magnetic study revealed that the complex ions were magnetically isolated from each other. Practically no 4f–4f superexchange interaction was operative, while the 2p–3d ferromagnetic coupling seemed to be appreciable, as anticipated from the proposed magnetostructural relationship. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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10 pages, 3711 KiB  
Article
Synthesis, Crystal Structure, and Luminescent Properties of a New Holmium(III) Coordination Polymer Involving 2,5-Dihydroxy-1,4-terephthalic Acid Dianion as Ligand
by Jiaqi Li, Linan Dun, Fanming Zeng, Chun Li and Zhongmin Su
Crystals 2021, 11(11), 1294; https://doi.org/10.3390/cryst11111294 - 26 Oct 2021
Cited by 2 | Viewed by 2540
Abstract
A novel coordination polymer {[Ho2(DHTA)3(H2O)5]·H2O}n (1) was synthesized by hydrothermal synthesis (DHTA = 2,5-dihydroxy-1,4-terephthalic acid anion). The crystallographic data show that complex 1 crystallizes in a triclinic system with space group P [...] Read more.
A novel coordination polymer {[Ho2(DHTA)3(H2O)5]·H2O}n (1) was synthesized by hydrothermal synthesis (DHTA = 2,5-dihydroxy-1,4-terephthalic acid anion). The crystallographic data show that complex 1 crystallizes in a triclinic system with space group P1¯, with a = 9.6617(17) Å, b = 11.902(2) Å, c = 13.284(2) Å, α = 100.617(3)°, β = 92.765(2)°, γ = 106.715(2)°, V = 1429.6(4) Å3, Z = 2, C24H24O24Ho2, and Mr = 1026.290. Complex 1 contains two eight-coordinated metal centers Ho(III). The TGA results show that the weight loss can be ascribed to the removal of the organic component from 400 to 650 °C. At the temperature above 650 °C, the residue is Holmium(III) oxide (Ho2O3). The luminescent results reveal that the complex has potential application as a new green luminescence material. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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Figure 1

15 pages, 5020 KiB  
Article
Heteroleptic [Cu(P^P)(N^N)][PF6] Complexes: Effects of Isomer Switching from 2,2′-biquinoline to 1,1′-biisoquinoline
by Nina Arnosti, Marco Meyer, Alessandro Prescimone, Edwin C. Constable and Catherine E. Housecroft
Crystals 2021, 11(2), 185; https://doi.org/10.3390/cryst11020185 - 13 Feb 2021
Cited by 6 | Viewed by 2776
Abstract
The preparation and characterization of [Cu(POP)(biq)][PF6] and [Cu(xantphos)(biq)][PF6] are reported (biq = 1,1′-biisoquinoline, POP = bis(2-(diphenylphosphanyl)phenyl)ether, and xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane). The single crystal structure of [Cu(POP)(biq)][PF6] 0.5Et2O was determined and compared to that [...] Read more.
The preparation and characterization of [Cu(POP)(biq)][PF6] and [Cu(xantphos)(biq)][PF6] are reported (biq = 1,1′-biisoquinoline, POP = bis(2-(diphenylphosphanyl)phenyl)ether, and xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane). The single crystal structure of [Cu(POP)(biq)][PF6] 0.5Et2O was determined and compared to that in three salts of [Cu(POP)(bq)]+ in which bq = 2,2′-biquinoline. The P–C–P angle is 114.456(19)o in [Cu(POP)(biq)]+ compared to a range of 118.29(3)–119.60(3)o [Cu(POP)(bq)]+. There is a change from an intra-POP PPh2-phenyl/(C6H4)2O-arene π-stacking in [Cu(POP)(biq)]+ to a π-stacking contact between the POP and bq ligands in [Cu(POP)(bq)]+. In solution and at ambient temperatures, the [Cu(POP)(biq)][PF6]+ and [Cu(xantphos)(biq)]+ cations undergo several concurrent dynamic processes, as evidenced in their multinuclear NMR spectra. The photophysical and electrochemical behaviors of the heteroleptic copper (I) complexes were investigated, and the effects of changing from bq to biq are described. Short Cu···O distances within the [Cu(POP)(biq)]+ and [Cu(xantphos)(biq)]+ cations may contribute to their very low photoluminescent quantum yields. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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Review

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20 pages, 1911 KiB  
Review
When the Metal Makes the Difference: Template Syntheses of Tridentate and Tetradentate Salen-Type Schiff Base Ligands and Related Complexes
by Rita Mazzoni, Fabrizio Roncaglia and Luca Rigamonti
Crystals 2021, 11(5), 483; https://doi.org/10.3390/cryst11050483 - 26 Apr 2021
Cited by 21 | Viewed by 4169
Abstract
The reaction of organic molecules mediated by a metal center (template synthesis) can result in a final connectivity that may differ from the one obtained in the absence of the metal. The condensation of carbonyl fragments with primary amines form C=N [...] Read more.
The reaction of organic molecules mediated by a metal center (template synthesis) can result in a final connectivity that may differ from the one obtained in the absence of the metal. The condensation of carbonyl fragments with primary amines form C=N iminic bonds, the so-called Schiff bases, which can act as ligands for the templating metal center by means of the lone pair on the nitrogen atom. This review focuses on the template methods for the reaction between a carbonyl compound (mainly salicylaldehyde) and a primary aliphatic diamine able to prevent the double condensation on both amine groups and obtain tridentate N2O ligands. These adducts, still having one free amino group, can further react, yielding tetradentate salen-type Schiff base ligands. A screening over the transition metals able to show such a template effect will be presented, with particular attention to copper(II), together with their peculiar reactivity and the available crystal structure of the metal complexes and related coordination geometries. Full article
(This article belongs to the Special Issue Self-Assembled Complexes: “Love at First Sight”)
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