Theoretical Study of Metallophilic Interactions and Excited States of Heterobimetallic d<sup>10</sup>−d<sup>8</sup> Complexes with Bridging Ligands: The Tuning of Electronic Spectroscopy

Pan, Qing‐Jiang; Guo, Yuan‐Ru; Zhang, Hongxing

doi:10.1021/om100080u

Cited by 14 publications

(7 citation statements)

References 100 publications

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“…1 Theoretical studies based on Pyykkö's work have estimated the metallophilic attraction to be approximately 10 kcal mol -1 , with minor variations depending on the specific compound. 2,[72][73][74][75] It should be noted that a more recent DFT study by Otero-de-la-Roza et al suggests that dispersion interaction is not as important a component in metallophilic attraction as suggested by Pyykkö, and is of relatively similar magnitude for all metals, with the total interaction energy ranging from 4 to 8 kcal mol -1 . 21 We have studied our systems using several methods and techniques in order to determine the physical origin of the intermetallic interaction in the studied complexes.…”

Section: Discussionmentioning

confidence: 91%

“…In contrast, the second school of thought, led by Pyykkö, claims that closed shell intermetallic interactions are mainly dispersive interactions . Theoretical studies based on Pyykkö’s work have estimated the metallophilic attraction to be approximately 10 kcal mol –1 , with minor variations depending on the specific compound. ,− It should be noted that a more recent DFT study by Otero-de-la-Roza et al suggests that dispersion interaction is not as important a component in metallophilic attraction as suggested by Pyykkö and is of relatively similar magnitude for all metals, with the total interaction energy ranging from 4 to 8 kcal mol –1 …”

Section: Discussionmentioning

confidence: 97%

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Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

2017

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Metallophilic interactions stabilize the bond between closed-shell metal centers, which electrostatically repel one another. Since its introduction, the origin of this interaction has been argued to be either London dispersion forces or dative bonding, but as yet there is no definitive answer. Insight into the nature of metallophilic bonding would provide the key for rational tuning of the stabilizing interaction, for example, in specific transmetalation transition states. We now report on a computational study focused on the metallophilic d 8 -d 10 bond in recently published families of Pd(II)-Cu(I) and Pd(II)-Zn(II) heterobimetallic compexes. We show that dative bonding outweighs dispersion interaction in controlling the metallophilic bonding energy in the studied heterobimetallic complexes, and elucidate the governing orbital interactions.suggested that the compound is a Lewis acid-base complex. 3 This Lewis acid-base description of the metallophilic bonds gained general popularity and these types of complexes are now often referred to as Metal-Only Lewis Pairs. Moret has reviewed this type of bonding for specific cases in which Pd(II) and Pt(II) are the d 8 components, 4 and presents the respective square-planar complexes as two-electron donors, with the dz2 orbital available to form dative bonds to Lewisacidic metals. Dewhurst and coworkers have recently published a broader review on Metal-Only Lewis Pairs and point out that discerning different types of bonding between transition metals is not easy, because the overall bonding interaction may comprise several components, such as ionic, covalent, dative, and closed-shell interactions. 5 An alternative description of the metallophilic bonding was proposed by Pyykkö, who, based on his studies on aurophilicity (attraction between Au cations), ascribed the attraction to a dispersion effect, i.e. an effect stemming from the correlated motion of electrons. 1,6 In addition to its fundamental value in chemical bonding theory, more detailed knowledge regarding the nature of metallophilic interaction has potential applicability in several fields of chemistry, e.g. supramolecular design 7 or catalysis. A relevant example was recently reported by Espinet, with regard to metallophilic interaction in heterobimetallic complexes and transitionmetal catalyzed cross-coupling catalysis. In a series of studies on the Pd-catalyzed Negishi crosscoupling, Espinet and coworkers proposed that the bonding interaction between an electron-rich Pd(II) and positively-charged Zn(II) in the transmetalation transition state (TS) is responsible for lowering the reaction barrier, which leads to reversible transmetalation and undesired homocoupling. [8][9][10][11] Similarly, the favorable metal-metal interaction between Pd(II) and Cu(I) in the transmetalation TS of the Sonogashira cross-coupling has been used to rationalize the low rearrangement barriers. 12 Insight into the nature of the intermetallic attraction would provide the foundation for tuning the interaction energy and, in turn, the ...

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Section: Discussionmentioning

confidence: 91%

Section: Discussionmentioning

confidence: 97%

Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

2017

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“…29,[38][39] In conjunction with experimental exploration, theoretical studies are helpful in designing dyes that have both high extinction coefficient and better overlap with the solar spectrum, ensuring improvements in the overall conversion efficiency of the DSSC. Investigations on several gold and platinum complexes [40][41][42] as well as Ru(II) dyes [38][39][43][44][45][46][47] indicated that density functional theory associated with reasonable solvation models is quite reliable for investigating their electronic spectra and energetics.…”

Section: Introductionmentioning

confidence: 99%

Structures, spectroscopic properties and redox potentials of quaterpyridyl Ru(ii) photosensitizer and its derivatives for solar energy cell: a density functional study

Pan

Guo

et al. 2011

Phys. Chem. Chem. Phys.

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Scalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans-[Ru((R)L)(NCS)(2)] ((R)L = 4,4'''-di-R-4',4''-bis(carboxylic acid)-2,2' : 6',2'' : 6'',2'''-quaterpyridine, R = H (1), Me (2), (t)Bu (3) and COOH (4); (R)L = 4,4'''-di-R-4',4''-bis(carboxylic acid)-cycloquaterpyridine, R = COOH (5)). The geometries of the molecular ground, univalent cationic and triplet excited states of 1-5 were optimized. In complexes 1-4, the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the C≡N-Ru angle representing the SCN → Ru coordination approaches 180° in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN → Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS → polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3, agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of π* character in the quaterpyridine ligand in 4. This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 1-5 were calculated and discussed, in conjunction with photosensitizers such as cis-[Ru(L(1))(2)(X)(2)] (L(1) = 4,4'-bis(carboxylic acid)-2,2'-bipyridine; X = NCS(-) (6), Cl(-) (7) and CN(-) (8)), cis-[Ru(L(1)')(2)(NCS)(2)] (L(1)' = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9), [NH(4)][Ru(L(2))(NCS)(3)] (L(2) = 4,4',4''-tris(carboxylic acid)-2,2' : 6',2''-terpyridine, 10) and [Ru(L(2))(NCS)(3)](-) (11).

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“…doi:10.1016/j.cplett.2011.03.016 density functional theory (TD-DFT) [15][16][17] with the same B3LYP functional was performed to calculate absorption spectra of complexes. Considering the influence of solvent on electronic spectra as indicated in our previous studies [18][19][20], we employed the conductor-like polarizable continuum model (CPCM) [21] to account for the solvent effect of methanol. We carried out the Hay and Wadt [22,23] effective core potentials (ECPs) calculations for Ru and S. The LANL2DZ basis sets associated with the ECPs were employed.…”

Section: Computational Detailsmentioning

confidence: 99%

Structures and spectroscopic properties of ruthenium phenanthroline solar-cell sensitizers: A computational study

Gao

Pan

et al. 2011

Chemical Physics Letters

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Theoretical Study of Metallophilic Interactions and Excited States of Heterobimetallic d¹⁰−d⁸ Complexes with Bridging Ligands: The Tuning of Electronic Spectroscopy

Abstract: A series of heterobimetallic d 10 -d 8 complexes, [

Cited by 14 publications

References 100 publications

Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

Structures, spectroscopic properties and redox potentials of quaterpyridyl Ru(ii) photosensitizer and its derivatives for solar energy cell: a density functional study

Structures and spectroscopic properties of ruthenium phenanthroline solar-cell sensitizers: A computational study

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Theoretical Study of Metallophilic Interactions and Excited States of Heterobimetallic d10−d8 Complexes with Bridging Ligands: The Tuning of Electronic Spectroscopy

Abstract: A series of heterobimetallic d 10 -d 8 complexes, [

Cited by 14 publications

References 100 publications

Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes

Structures, spectroscopic properties and redox potentials of quaterpyridyl Ru(ii) photosensitizer and its derivatives for solar energy cell: a density functional study

Structures and spectroscopic properties of ruthenium phenanthroline solar-cell sensitizers: A computational study

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Theoretical Study of Metallophilic Interactions and Excited States of Heterobimetallic d¹⁰−d⁸ Complexes with Bridging Ligands: The Tuning of Electronic Spectroscopy