Molecular Design of Organometallic Materials: Effect of the Metallophilic Interactions, Ligand, Metal, and Oxidation State

Romanova, Julia; Prabhath, M. R. Ranga; Sadik, Yousif; Jarowski, Peter D.

doi:10.1007/978-3-319-50255-7_8

Cited by 4 publications

(8 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The series of six complex ions have been selectively chosen so that the nitrogen content and the nitrogen position in the X ligand can be varied systematically. We have shown in our laboratories that systematic efforts to modify structural aspects of optical materials yield important design criteria and here we apply this strategy to excited state engineering in Ru–polypyridyl complex ions. − Three of these complex ions, 12PYAZ, 12PZAZ, and 13PZAZ, are computationally designed in our laboratory and have not been reported previously. The other three complex ions that form part of this study, 13PYAZ, 124PYAZ, and 124PZAZ, are already known in the literature, ,,− which helps to benchmark our calculations as well as to provide further insight into the emission mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…The results are obtained by the density functional theory (DFT) and its time-dependent (TD) formulation in combination with PBE0 functional and a polarizable continuum model (PCM) of the solvent. The same computational strategy was recently applied in our laboratory with great effect in the design of platinum complexes with tunable luminescence properties. − …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Engineering Tunable Single and Dual Optical Emission from Ru(II)–Polypyridyl Complexes through Excited State Design

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Engineering Tunable Single and Dual Optical Emission from Ru(II)–Polypyridyl Complexes through Excited State Design

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…The same computational strategy was recently successfully applied in our laboratory in the design of platinum and ruthenium complexes with tunable luminescence properties. [35][36][37][38] All quantum-chemical calculations were performed with the Gaussian 09 program package. 39 The molecular orbitals were visualized with an isosurface value of 0.04 by using GaussView 5 graphical interface.…”

Section: Computational Proceduresmentioning

confidence: 99%

“…Absorption and emission properties were obtained by the time-dependent formulation of density functional theory (TD-DFT) with the same functional, basis sets and solvation model as for ground state geometry optimization. The same computational strategy was recently successfully applied in our laboratory in the design of platinum and ruthenium complexes with tunable luminescence properties. − All quantum-chemical calculations were performed with the Gaussian 09 program package . The molecular orbitals were visualized with an isosurface value of 0.04 by using the GaussView 5 graphical interface…”

Section: Computational Proceduresmentioning

confidence: 99%

Molecular Design of pH-Sensitive Ru(II)–Polypyridyl Luminophores

Romanova

Sadik²,

Prabhath³

et al. 2019

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

Three new [Ru(bpy)2X] + complex ions, where bpy represents bipyridyl ligand and X denotes pH-sensitive pyridyl diazolate or pyrazinyl diazolate coordination site, have been computationally designed and synthesised as pH sensitive molecules. The choice of pyridyl and pyrazinyl moieties allows for the nitrogen content to vary, while the influence of the protonation site is quantified by using 1,2-diazolate and 1,3-diazolate derivatives. The absorption and emission properties of the deprotonated and protonated complex ions were characterised by UV-vis and photoluminescence spectroscopy, as well as by time-dependent density functional theory.Protonation causes (1) a strong blue shift in the lowest energy 3 MLCT→S0 emission wavelengths,(2) a substantial increase in the emission intensity and (3) a change in the character of the corresponding 3 MLCT emitting states. The blue shift in the emission wavelength becomes less pronounced when the nitrogen content in the X ligand increases and when going from 1,2-to 1,3diazolate derivatives. The contrast in the emission intensity of the protonated/deprotonated forms is highest for the complex ion, containing 2-pyridyl derivative of the 1,2-diazolate. The complex ions are suggested as potential pH-responsive materials based on change in the colour and intensity of the emitted radiation. The broad impact of the research is that demonstrate that the modification of the nitrogen content and position within the protonable ligands is an effective approach for modulation of the pH-optosensing properties of Ru-polypyridyl complexes.

show abstract

“…Furthermore, the photoluminescent characters might be modulated as metallophilic interaction changed by the functional guest molecules/ions introduced into the M···M interaction systems. Some groups [ 4 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 ] have made significant progress in this area. For example, Catalano et al introduced BF 4 − and CH 3 OH through anion-cation/anion–π interaction to the hetero-metallic coordinated [AuCu-(PPh 2 py) 3 ](BF 4 ) 2 Au(I)···Cu(I) complex [ 4 ].…”

Section: Introductionmentioning

confidence: 99%

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation

Yang

et al. 2018

Nanomaterials

View full text Add to dashboard Cite

MP2 (Second order approximation of Møller–Plesset perturbation theory) and DFT/TD-DFT (Density functional theory/Time-dependent_density_functional_theory) investigations have been performed on metallophilic nanomaterials of host clusters [Au(NHC)2]+⋅⋅⋅[M(CN)2]−⋅⋅⋅[Au(NHC)2]+ (NHC = N-heterocyclic carbene, M = Au, Ag) with high phosphorescence. The phosphorescence quantum yield order of clusters in the experiments was evidenced by their order of μS1/ΔES1−T1 values (μnormalS1: S0 → S1 transition dipole, ∆EnormalS1−normalT1: splitting energy between the lowest-lying singlet S1 and the triplet excited state T1 states). The systematic variation of the guest solvents (S1: CH3OH, S2: CH3CH2OH, S3: H2O) are employed not only to illuminate their effect on the metallophilic interaction and phosphorescence but also as the probes to investigate the recognized capacity of the hosts. The simulations revealed that the metallophilic interactions are mainly electrostatic and the guests can subtly modulate the geometries, especially metallophilic Au⋅⋅⋅M distances of the hosts through mutual hydrogen bond interactions. The phosphorescence spectra of hosts are predicted to be blue-shifted under polar solvent and the excitation from HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) was found to be responsible for the 3MLCT (triplet metal-to-ligand charge transfer) characters in the hosts and host-guest complexes. The results of investigation can be introduced as the clues for the design of promising blue-emitting phosphorescent and functional materials.

show abstract

Molecular Design of Organometallic Materials: Effect of the Metallophilic Interactions, Ligand, Metal, and Oxidation State

Cited by 4 publications

References 62 publications

Engineering Tunable Single and Dual Optical Emission from Ru(II)–Polypyridyl Complexes through Excited State Design

Engineering Tunable Single and Dual Optical Emission from Ru(II)–Polypyridyl Complexes through Excited State Design

Molecular Design of pH-Sensitive Ru(II)–Polypyridyl Luminophores

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation

Contact Info

Product

Resources

About