Organometallic complexes as luminescence probes in monitoring thermal and photochemical polymerizations

Lees, Alistair J.

doi:10.1016/s0010-8545(98)00099-x

Cited by 78 publications

(47 citation statements)

References 64 publications

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“…On the basis of data from ref. [94][95][96][97][98][99][100][101] we obtain the correlation shown in Figure 5. The relation E MLCT = f(ModEP) is linear and is described by Equation (8).…”

Section: M(diimine)(co) 4 (M = W Mo Cr)mentioning

confidence: 85%

“…These compounds are known for their negative solvatochromism and luminescence in solution and find potential applications in material science. [94][95][96][97][98][99][100][101] They have a solvatochromic band that is attributed to a MLCT transition. On the basis of data from ref.…”

Section: M(diimine)(co) 4 (M = W Mo Cr)mentioning

confidence: 99%

“…[95,102] [103][104][105][106] These complexes have a diimine-based reversible reduction process. We tested the ModEP scale, searching for a correlation of the type E red = f(ModEP).…”

Section: Fac-[re(co) 3 (Cnx)(diimine)]mentioning

confidence: 99%

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Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

Makedonas

Mitsopoulou

2007

Eur J Inorg Chem

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In order to quantify the contribution of mainly, but not only, diimine ligands to the electronic properties of the corresponding complexes, two novel indices, namely modified electronic parameters (ModEP) and electrophilicity, ω, are introduced and discussed in this report. First, we introduce the concept of ModEP, a novel scale relating to the electronic properties of diimine ligands. Mainly on the basis of wellcharacterized M(diimine)(dithiolato) complexes (M = Pt, Pd, or Ni), we derive the contribution of the diimine ligand to the reduction potentials of the complexes, and incorporating its contribution to the main charge-transfer band of the UV/Vis spectra, we obtain our ModEP values. The applicability of the introduced scale to several other classes of diimine compounds (W, Re, and Ru) is then tested. The performance of our scale in predicting the values of the reduction potentials and the position of the charge-transfer bands is very satisfactory. With this approach, some interesting aspects of ligand

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“…On the basis of data from ref. [94][95][96][97][98][99][100][101] we obtain the correlation shown in Figure 5. The relation E MLCT = f(ModEP) is linear and is described by Equation (8).…”

Section: M(diimine)(co) 4 (M = W Mo Cr)mentioning

confidence: 85%

Section: M(diimine)(co) 4 (M = W Mo Cr)mentioning

confidence: 99%

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Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

Makedonas

Mitsopoulou

2007

Eur J Inorg Chem

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“…[1][2][3] These compounds combine an electron-rich, low-valent, typically d 6 metal atom, which is stabilized by the presence of four carbonyl groups along with the good π*-accepting α-diimine ligand. The observed lowest lying MLCT state is responsible for several interesting features, such as the negative solvatochromism and the solution luminescence, while it is associated with large, second-order molecular hyperpolarizabilities.…”

Section: Introductionmentioning

confidence: 99%

“…This state arises from the transition between a metal/CO localized HOMO-2 and a diimine LUMO (both of b 1 symmetry in the case of the C 2v point group). [4,5] Thus the electronic properties of M(CO) 4 (diimine) make their use quite essential in areas such as the investigation of polymerization processes, [2] the labeling of biomolecules, [6] and the exploitation of solar energy. [7] All the structures of tetracarbonyl diimine compounds, which are either crystallographically elucidated or theoretically predicted, share two common features.…”

Section: Introductionmentioning

confidence: 99%

W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Makedonas

Mitsopoulou

2006

Eur J Inorg Chem

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The bending of axial and equatorial carbonyls, one of the main structural features of the M(CO) 4 (diimine) compounds (M = Cr, Mo, and W), is elucidated in terms of the π* backbonding theory by a frontier molecular orbital analysis. Employing W(CO) 4 (phen) (phen = 1,10-phenanthroline) as a reference compound has proved that the deviation from orthogonality stabilizes the structure by a total amount of 2.95 kJ/ mol. Moreover, by an extended comparison of several W(CO) 4 (diimine) structures, the importance of the magnitude of the binding angle in determining the bonding in these complexes in comparison to the traditional approach of the W-C and C-O bond lengths is underlined. As a result, it is

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Luminescence Behavior & Photochemistry of Organotransition Metal Compounds

Yam

2005

Encyclopedia of Inorganic Chemistry

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In this article, the luminescence and photochemical properties of a selection of organotransition metal compounds are reviewed and discussed. The examples are classified according to the identity of the carbon‐containing ligands, which include the carbonyl, isocyanide, cyanide, alkynyl, alkenyl, arene, aryl, alkylidene, alkylidyne, cyclometalating, and alkyl ligands. The luminescence and photochemistry of selected tungsten, molybdenum, and rhenium carbonyl compounds are described in this article, followed by some examples with the analogous isocyanide and cyanide ligands. The luminescence properties and potential applications of these systems are discussed. Transition metal complexes containing alkynyl ligands display a very wide structural diversity and catalytic properties, and many systems also show intriguing photoluminescence properties, especially those of rhenium(I), platinum(II), palladium(II), and the coinage metals. Studies focused on the photophysical studies and the excited‐state chemistry of selected alkynyl systems and related alkenyl, arene, and aryl complexes are outlined and discussed. Luminescent metal–carbon multiple bonded systems including the alkylidene and alkylidyne compounds have received relatively little attention, and examples have been confined to the complexes of molybdenum and tungsten. However, much effort has recently been devoted to exploring the interesting emission properties of alkylidene and alkylidyne systems with other metal centers such as rhenium, ruthenium, osmium, platinum, and coinage metals, which are outlined in this article. Some recent examples in the areas of cyclometalated complexes, especially those of rhodium(III), iridium(III), platinum(II), and gold(III) centers are highlighted in this article as many examples display impressive photophysical and photochemical behavior. Metal alkyl systems represent a special class of luminescent organometallic system due to their strong σ‐donating properties of the alkyl ligands, and the photophysical and excited‐state properties of some selected examples are described. Finally, luminescent organotransition metal compounds with application potentials in the development of new materials, photodevices, and sensory systems are summarized in various parts of this article.

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Organometallic complexes as luminescence probes in monitoring thermal and photochemical polymerizations

Cited by 78 publications

References 64 publications

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Luminescence Behavior & Photochemistry of Organotransition Metal Compounds

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Organometallic complexes as luminescence probes in monitoring thermal and photochemical polymerizations

Cited by 78 publications

References 64 publications

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

W(CO)4(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Luminescence Behavior & Photochemistry of Organotransition Metal Compounds

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Product

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W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding