Solid state conformational preferences in transition metal complexes double bridged by phosphate and related ligands

Pérez, Jose; Garcı́a, Luis; Carrascosa, Ramón; Pérez, Eduardo; Serrano, José Luís

doi:10.1016/j.poly.2008.04.053

Cited by 8 publications

(4 citation statements)

References 19 publications

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“…Each silver atom is μ 2 -bridged by the sulfur atoms belonging to two different ligands to give rise to eight-membered metallarings having ‘ twist-chair ’ ( 2 ) or ‘ chair ’ ( 4 ) conformations (Table S1, Supporting Information), as shown in Figure . In these rings, the silver−silver distances [Ag(1)−Ag(2) a 3.3289(6) Å in 2 (a: 1 − x , 1 − y , 1 − z ) and Ag(1)−Ag(2) 3.3966(5) Å in 4 ] are, although longer than in metallic silver [2.889(6) Å], shorter than twice the van der Waals radius of this metal (3.44 Å), and in light of previous works, − this suggests the existence of significant Ag−Ag interactions.…”

Section: Resultsmentioning

confidence: 64%

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles

Castiñeiras

Pedrido

2009

Inorg. Chem.

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The reaction of silver acetate and silver nitrate with the new phosphinethiosemicarbazone ligand 2-(2-(diphenylphosphino)benzylidene)-N-ethylthiosemicarbazone (HLPEt) gave rise to the complexes [Ag(LPEt)](4).2MeOH (1) and [Ag(2)(LPEt)(HLPEt)](2).(NO(3))(2) (3). Slow crystallization of the mother liquors obtained from the synthesis of 1 and 3 afforded suitable crystals of [Ag(2)(LPEt)(HLPEt)](2)(CH(3)COO)(2).6MeOH (2) and [Ag(2)(LPEt)(HLPEt)](2)(NO(3))(2).2MeOH.2H(2)O (4), respectively. Complexes 2 and 4 are tetranuclear silver clusters displaying a similar Ag(4)S(4)P(4) core, but containing different sizes, conformations for the Ag(4)S(4) metallacycles, and crystal packings. The four complexes are strongly luminescent in methanol solutions. A comparison between the emission bands of compounds 1-4 lead us to conclude that the luminescence is notably affected by the charge and the counterion of the cluster.

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Section: Resultsmentioning

confidence: 64%

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles

Castiñeiras

Pedrido

2009

Inorg. Chem.

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“…With only one possible outlier, all of the rings examined adopted a square-like conformation with D 2 symmetry. Pérez et al investigated the conformations of the 8-membered ring in the [M(μ-OPO)] 2 core of complexes in which transition metals (M) are double bridged by phosphate and related groups . The large number of CSD structures containing this fragment made it possible to reach detailed conclusions that we suspect would have been difficult to obtain in any other way.…”

Section: Fundamental Sciencementioning

confidence: 99%

A Million Crystal Structures: The Whole Is Greater than the Sum of Its Parts

2019

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The founding in 1965 of what is now called the Cambridge Structural Database (CSD) has reaped dividends in numerous and diverse areas of chemical research. Each of the million or so crystal structures in the database was solved for its own particular reason, but collected together, the structures can be reused to address a multitude of new problems. In this Review, which is focused mainly on the last 10 years, we chronicle the contribution of the CSD to research into molecular geometries, molecular interactions, and molecular assemblies and demonstrate its value in the design of biologically active molecules and the solid forms in which they are delivered. Its potential in other commercially relevant areas is described, including gas storage and delivery, thin films, and (opto)electronics. The CSD also aids the solution of new crystal structures. Because no scientific instrument is without shortcomings, the limitations of CSD research are assessed. We emphasize the importance of maintaining database quality: notwithstanding the arrival of big data and machine learning, it remains perilous to ignore the principle of garbage in, garbage out. Finally, we explain why the CSD must evolve with the world around it to ensure it remains fit for purpose in the years ahead.

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“…2. The results show (Table 1) that in most of the fragments (85% of cases) the organic ligands adopt a similar conformation that can be described as follows: the ring containing the C=N bond adopts a distorted half-chair conformation (ring 1), the ring defined by both the N-sp 3 shows a distorted envelope conformation (ring 2), and the remaining ring exhibits a chair conformation (ring 3). Fig.…”

Section: Conformational Preferencesmentioning

confidence: 94%

“…We have recently contributed to this field in some of the above mentioned aspects. [2][3][4] Focusing on organic compounds as ligands, it must be pointed out that the coordination upon metal centres modifies the properties of the free organic molecule in several aspects, 5 including important structural changes. Thus, the conformation of small molecules, such as carbon disulphide, acetylene or butadiene, in transition metal complexes has been widely analysed, 6 showing that the geometry in complexes is similar to that in excited states and therefore different from its electronic ground state.…”

Section: Introductionmentioning

confidence: 99%

Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

et al. 2011

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The solid state conformational preferences of ligand 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene (L1) and its 9-methyl derivative (L2) in transition metal complexes have been determined by a probabilistic method using data retrieved from the Cambridge Structural Database. These macrocyclic compounds, as ligands, tend to adopt a preferential conformation (85% of cases). The ring containing the C=N bond adopts a distorted half-chair conformation, the ring defined by both the N-sp(3) shows a distorted envelope conformation, and the remaining ring exhibits a chair conformation. This conformation corresponds to the enantiomer pair R(N5)S(N9)S(P)/S(N5)R(N9)R(P). Molecular mechanics calculations demonstrate that this is a high energy conformation for the organic molecule, far from the energy minimum. Two other enantiomer pairs are observed in experimental structures. The influence of the coordination on the conformation of the organic ligands has been studied by DFT calculations, and a clear correlation with the geometry of the coordination sphere has been found.

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Solid state conformational preferences in transition metal complexes double bridged by phosphate and related ligands

Cited by 8 publications

References 19 publications

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles

A Million Crystal Structures: The Whole Is Greater than the Sum of Its Parts

Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

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Solid state conformational preferences in transition metal complexes double bridged by phosphate and related ligands

Cited by 8 publications

References 19 publications

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag4S4 Metallacycles

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag4S4 Metallacycles

A Million Crystal Structures: The Whole Is Greater than the Sum of Its Parts

Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

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Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles

Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag₄S₄ Metallacycles