Metal–Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes

Galembeck, Sérgio E.; Caramori, Giovanni F.; Misturini, Alechania; Garcia, Leone C.; Orenha, Renato Pereira

doi:10.1021/acs.organomet.7b00393

Cited by 12 publications

(15 citation statements)

References 52 publications

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“…Metal‐ligand interactions play important roles in nanocrystals, molecular recognition, drug design, metalloprotein chemistry, and so on. Both GKS‐EDA and LMO‐EDA have been employed in the interpretations of various metal‐ligand interactions, which are not trivial tasks due to the inherent complexity of the arrangement of electrons in d‐ and f‐metal‐atom orbitals coupled with the various ligands.…”

Section: Applicationsmentioning

confidence: 99%

Generalized Kohn‐Sham energy decomposition analysis and its applications

Tang

2020

WIREs Comput Mol Sci

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Energy decomposition analysis (EDA) methods bridge the gap between electronic structure calculations and conceptual interpretations of molecular interactions. The recently developed generalized Kohn‐Sham EDA (GKS‐EDA) can be used to examine various molecular interactions with restricted, restricted open‐shell or unrestricted Kohn‐Sham orbitals. It supports different density functional theory functionals, including LDA, GGA, hybrid, double hybrid, range‐separated, and dispersion‐corrected density functionals. GKS‐EDA can be also efficiently applied for intermolecular interactions in solutions and intramolecular interactions when used in combination with an implicit solvation model and appropriate fragmentation method. GKS‐EDA helps us not only to understand but also to predict the structures and properties of various interacting systems within a unified approach. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Molecular and Statistical Mechanics > Molecular Interactions Electronic Structure Theory > Density Functional Theory Structure and Mechanism > Molecular Structures

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Section: Applicationsmentioning

confidence: 99%

Generalized Kohn‐Sham energy decomposition analysis and its applications

Tang

2020

WIREs Comput Mol Sci

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“…is considered a poor R group to host anions, [20] and s-triazine (TRZ) lies on the borderline between being able to interact with both cations and anions, [107][108][109] cyanuric acid (CA), on the other hand, is a very good anion receptor due to its π-acidic nature, and in fact has proved to be so. [20,23,40] Despite this fact, BZN and TRZ are known as good π-systems to form metal complexes, and such metal-R complexes have proved to be effective in tuning the aromatic system to become electron deficient, [24,60,61,110] hence BZN and TRZ should be considered good candidates to form novel π-metallated cylindrophane systems ideally including NH þ 2 groups in the bridges to coordinate anions. Figure 5, correlating H to HG in the H!…”

Section: Structural Parameters and Geometry Analysesmentioning

confidence: 99%

“…Attention has increasingly been given to receptors capable of selectively recognizing and coordinating fluoride, [58,59] highlighting the challenges intrinsic to anion coordination in aqueous systems, often involving the synthesis of metallated receptors that interact strongly with anions. [25,60,61]…”

Section: Introductionmentioning

confidence: 99%

“…Ultimately, numerous anion‐ π based studies have led to the development of novel supramolecular systems as well as advances in catalysis, medicinal chemistry, and biochemistry, all of which support the continued drive to gain insight into this specific NCI . Attention has increasingly been given to receptors capable of selectively recognizing and coordinating fluoride, highlighting the challenges intrinsic to anion coordination in aqueous systems, often involving the synthesis of metallated receptors that interact strongly with anions …”

Section: Introductionmentioning

confidence: 99%

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In Silico Design of Cylindrophanes: The Role of Functional Groups in a Fluoride Selective Host

et al. 2020

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Molecular recognition is the key driver in the formation of supramolecular complexes, enabling the selective encapsulation of specific guests. Here, we explore the delicate balance between different energetic terms in the formation of an efficient host for fluoride anions based on a cylindrophane structure, which can be achieved by the incorporation of ligand sites into a cyanuric acid based cyclophane framework, resulting a close proximity between the ammonium hydrogens and the anion. This study describes the character and contribution of different energetic and repulsive terms that favor the efficient inclusion of fluoride. Our findings are useful for further rational design and synthesis of efficient and highly selective fluoride hosts, which have been generally less well described than complexing agents for other halides.

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“…As discussed in the introduction, molecular rings such as cyclophanes have proven to be efficient hosts for metal ions in their cavities. 116,205,206 They make excellent host-guest interactions commonly known as π-prismands where the cavity adopts a prism-shaped geometry to accommodate the guest metal atom. 62,111 Previously, the reactivity and sensitivity of such host-guest complexes has been reported to change by replacing the aromatic ring with other different π-efficient hosts such as imidazolium.…”

Section: Coordination Of Cyclophanes With Heavier Main-group Metalsmentioning

confidence: 99%

Computational Chemistry of Compounds with Donor-Acceptor Interactions

Altaf¹

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<p>Compounds with donor-acceptor interactions find important applications in catalysis, C-H activation, phosphorus activation, selective oxidation and cyclization. Moreover, they are potential candidates for use in the synthesis of materials, polymers and light-harvesting systems. The efficient use of a chemical entity is possible when we know its structural and bonding properties. This computational study is intended for the same by studying in detail the structure and bonding properties of donor-acceptor complexes of heavier main-group metals with cyclophane ligands and some heterobimetallic complexes. Additionally, we explored the fluorescence characteristics of benzanthrone dyes. The first part (i.e. main group metal complexes) involves the exploration of structural features and thermal properties through DFT optimization and then calculating the change in enthalpy of formation for all the possibilities under consideration. For this purpose we selected the last three elements from each of Groups 13, 14 and 15 to explore their different coordination modes with two cyclophane ligands; [2.2.2]paracyclophane and deltaphane. We opted for chlorides of each metal to allow them to coordinate from outside the phenyl rings of the cyclophane cavity and from the top of the cavity. To see the coordination of the metals with the inner core of the selected cyclophanes, we put metal cations in the centre of the cavity and optimized. Subsequently, the bonding properties of these inclusion complexes have been analysed in detail on the basis of Morokuma-Ziegler energy decomposition analysis. Secondly, we investigated the structure and bonding properties of some indium-zinc heterobimetallic compounds through geometry optimization, NBO analysis and quantum theory of atoms in molecules (QTAIM) analysis--also known as Bader's analysis. We propose that the heterobimetallic reactant involves donor-acceptor bond that cleaves as a result of the addition of mesityl azide. The newly formed complex has In-N and Zn-N bonds. In the final part benzanthrone dyes containing intramolecular donor-acceptor interactions, (and hence, undergoing intramolecular charge transfer) were subject to the computational investigation of the mechanism of fluorescence taking place in them. Electronic excitations and the structure of first excited state in each case has been discussed thoroughly based on the time-dependent density functional theory. To check for the non-radiative loss of energy, we also performed calculations for the vertical excitations of the triplet states of all the molecules under study. To get a deeper insight into the intramolecular charge transfer, we performed NTO analysis that gives us information based on different colours in regions of charge accumulation and charge depletion.</p>

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Metal–Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes

Cited by 12 publications

References 52 publications

Generalized Kohn‐Sham energy decomposition analysis and its applications

Generalized Kohn‐Sham energy decomposition analysis and its applications

In Silico Design of Cylindrophanes: The Role of Functional Groups in a Fluoride Selective Host

Computational Chemistry of Compounds with Donor-Acceptor Interactions

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