Effect of intramolecular π–π and CH–π interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)3(PR3)]+(bpy = 2,2′-bipyridine; PR3= trialkyl or triarylphosphines)

Tsubaki, Hideaki; Tohyama, Shigeki; Koike, Kazuhide; Saitoh, Hirokazu; Ishitani, Osamu

doi:10.1039/b407947g

Cited by 85 publications

(75 citation statements)

References 63 publications

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“…To cancel the electronic effect, we can use Tol- mans c values, which are used as an index of the electronaccepting ability of phosphine ligands. [21,22,29] Figure 12a and b show the relationships of the oxidation potential E On the other hand, the redox potential attributed to reduction of the dmb ligand did not show a simple linear correlation with the Sc value, as shown in Figure 12b. We have reported that through-space interaction between the diimine ligand and the aryl group(s) in the phosphine ligands of fac-…”

Section: Structural Features Of Eta C H T U N G T R E N N U N G (Nm)mentioning

confidence: 78%

“…Synthesis of the rhenium(I) complexes EtA C H T U N G T R E N N U N G (n,m): The bisphosphine rhenium(I) complexes EtA C H T U N G T R E N N U N G (n,m) were synthesized through mono-phosphine-tricarbonyl-rhenium(I) complexes by the photoinduced ligand substitution reaction [21] as shown in Scheme 2. These complexes were isolated as the PF 6 À salts and purified by column chromatography on silica gel and/or recrystallization.…”

Section: Resultsmentioning

confidence: 99%

“…[20] Our group has recently reported that the intramolecular aromatic interaction is a unique and very useful method for controlling the various properties of rhenium(I) complexes. [21,22] The p-p interaction between the ligand 4,4'-dimethyl-2,2'-bipyridine (dmb) and the aryl groups of the phosphine ligands in cis,trans-[ReA C H T U N G T R E N N U N G (dmb)(CO) 2 …”

Section: Introductionmentioning

confidence: 99%

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Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction

Morimoto

Ito

Koike

et al. 2012

Chemistry A European J

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A series of rhenium(I) diimine complexes cis,trans-[Re(dmb)(CO)(2)(PR(1)R(2)R(3))(PR(4)R(5)R(6))](+) (dmb=4,4'-dimethyl-2,2'-bipyridine, R(n)=phenyl or alkyl), each of which bears two phosphine ligands with various numbers of phenyl groups, has been synthesized by using the photochemical ligand-substitution reaction. Detailed studies of the structural features, not only in the crystal but also in solution, indicate that the number of phenyl groups is a crucial factor in controlling the rotational conformation of the phosphine ligands, which in turn determines the extent of the π-π interaction between the aromatic diimine ligand and the phenyl group(s). The π-π interaction strongly affected both electrochemical and photophysical properties: 1) the oxidation power of the Re complex became stronger, 2) the lifetime of the excited state became longer, and 3) the Stokes shift between the (1) MLCT absorption band and emission from the corresponding (3) MLCT excited state became smaller. In particular, the diphenyl and triphenyl phosphine had much greater influence on the properties than the monophenyl phosphine ligand. Dual emission was observed from the different rotational conformers of the complexes with an intermediate number of phenyl groups in the phosphine ligands.

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Section: Structural Features Of Eta C H T U N G T R E N N U N G (Nm)mentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction

Morimoto

Ito

Koike

et al. 2012

Chemistry A European J

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“…ligands coordinated to a metal, can interact with a π-system. In addition, interactions named metal-ligand-aromatic cation-π interactions (MLACπ) [14][15][16][17][18][19], can be considered as a type of XH/π hydrogen bond [20][21][22]. It was shown that some of these interactions are among the strongest XH/π hydrogen bonds [18].…”

Section: Introductionmentioning

confidence: 99%

Influence of metal and ligand types on stacking interactions of phenyl rings with square-planar transition metal complexes

Sredojević

Tomić²,

Zarić

2007

Open Chemistry

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Abstract:In order to find out whether metal type influences the stacking interactions of phenyl rings in square-planar complexes, geometrical parameters for Cu, Ni, Pd and Pt complexes, with and without chelate rings, were analyzed and compared. By searching the Cambridge Structural Database, 220 structures with Cu complexes, 211 with Ni complexes, 285 with Pd complexes, and 220 with Pt complexes were found. The results show that the chelate ring has a tendency to make the stacking interaction with the phenyl ring independent of metal type in the chelate ring. However, there are some differences among metals for complexes without a chelate ring. There are a number of structures containing Pd and Pt complexes, without chelate rings, that have short carbon-metal distances and parallel orientations of the phenyl ring with respect to the coordination plane. It was found that some of these complexes have a common fragment, CN, as a part of the ligands. This indicates that the CN supports stacking interactions of square planar complexes with the phenyl ring.

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“…are the subject of intensive study as a new approach of developing materials science [1]. In coordination chemistry, these weak interactions are important in determining the conformations, the selectivities of the reactions, and the crystal structures of metal complexes [2]. The p -p and CH -p interactions are noncovalent forces which contribute to self-assembly and/or recognition processes when extended structures are formed from building blocks with aromatic moieties [3].…”

mentioning

confidence: 99%

Photophysical Processes in ‘Supramolecular Balls’ Formed by Lanthanide Chloride with 2,2′‐Bipyridine

Puntus

2009

Helvetica Chimica Acta

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With gratitude to Prof. Jean-Claude G. Bünzli for induced interest to supramolecular lanthanide chemistry The europium complex [EuCl 2 (bpy) 2 (H 2 O) 2 ]Cl · 1.25 C 2 H 6 O · 0.37 H 2 O, where bpy is 2,2'-bipyridine, was synthesized and investigated with the aim to relate its molecular geometry and crystal packing to the efficiency of energy-transfer processes. The presence of H-bonds between noncoordinated Cl À ions and coordinated H 2 O molecules leads to the formation of discrete trimers assembled by a number of CÀH ··· Cl and stacking interactions into supramolecular balls which contain Cl À ions and solvate molecules (H 2 O and EtOH). The additional stabilization of the complex is due to intramolecular N ··· C interactions between two bpy ligands that causes some shortening of the EuÀN bonds. Deciphering the luminescence properties of the Eu complex was performed under consideration of both the composition of the inner coordination sphere and the peculiarities of the crystal packing. The influence of the latter and the bpy orientation on the energy of the ligand ! Eu charge-transfer state (LMCT) was established, and an additional excited state induced by the p-stacking interaction (SICT) was identified.Introduction. -Weak noncovalent forces (H-bonding, coordination bonds, electrostatic and charge-transfer attractions, aromatic p-stacking interaction, etc.) are the subject of intensive study as a new approach of developing materials science [1]. In coordination chemistry, these weak interactions are important in determining the conformations, the selectivities of the reactions, and the crystal structures of metal complexes [2]. The p -p and CH -p interactions are noncovalent forces which contribute to self-assembly and/or recognition processes when extended structures are formed from building blocks with aromatic moieties [3]. Recently it has been reported that the photophysical properties of transition-metal complexes are affected by intermolecular p -p and CH -p interactions [4]. The introduction of rare-earth metals into self-assembling molecular architectures can lead to the design of advanced luminescent materials. The unique ability of the rare-earth metals to emit well-defined narrow bands in different spectral ranges from VIS to near-IR with relatively long lifetimes and high quantum yields [5] makes them perfect candidates for many fields of materials science. In spite of the fact that numerous lanthanide complexes have been intensively studied to find a method to manage the efficiency of photophysical processes, many questions of the influence of the supramolecular structure on the properties of the lanthanide systems are still open, and no systematic studies of the effect of noncovalent interactions on photophysical properties have been performed.The 2,2'-bipyridine (bpy) is a well known ligand of highly luminescent complexes with transition and rare-earth metals. In the former case, diimine complexes of

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Effect of intramolecular π–π and CH–π interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)₃(PR₃)]⁺(bpy = 2,2′-bipyridine; PR₃= trialkyl or triarylphosphines)

Cited by 85 publications

References 63 publications

Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction

Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction

Influence of metal and ligand types on stacking interactions of phenyl rings with square-planar transition metal complexes

Photophysical Processes in ‘Supramolecular Balls’ Formed by Lanthanide Chloride with 2,2′‐Bipyridine

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