Terpyridine Zn(ii), Ru(iii) and Ir(iii) complexes as new asymmetric chromophores for nonlinear optics: first evidence for a shift from positive to negative value of the quadratic hyperpolarizability of a ligand carrying an electron donor substituent upon coordination to different metal centres

Roberto, Dominique; Tessore, Francesca; Ugo, R.; Bruni, Silvia; Manfredi, Amedea; Quici, Silvio

doi:10.1039/b201221a

Cited by 56 publications

(56 citation statements)

References 19 publications

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“…[97][98][99][100][101][102][103][104] A detailed review about this concept has recently been published by Williams et al [105] Iridium(III) mono-terpyridine complexes decorated with electron-donor or -acceptor groups have furthermore been employed as asymmetric chromophores in nonlinear optics. [106,107] By introducing strong ligand-field-stabilizing ligands, such as CN À or CO, the energy gap between the HOMO and LUMO can be significantly increased resulting in anionic or cationic iridium(III) complexes with bright blue emission. Recent examples by Fantacci and Nazeeruddin and their co-workers [108,109] as well as Chin et al [110] have nicely expanded the toolbox of color-tuning in iridium(III) complexes (Scheme 2).…”

Section: Charged Iridium(iii) Complexesmentioning

confidence: 99%

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

et al. 2009

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The recent developments in using iridium(III) complexes as phosphorescent emitters in electroluminescent devices, such as (white) organic light‐emitting diodes and light‐emitting electrochemical cells, are discussed. Additionally, applications in the emerging fields of molecular sensors, biolabeling, and photocatalysis are briefly evaluated. The basic strategies towards charged and non‐charged iridium(III) complexes are summarized, and a wide range of assemblies is discussed. Small‐molecule‐ and polymer‐based materials are under intense investigation as emissive systems in electroluminescent devices, and special emphasis is placed on the latter with respect to synthesis, characterization, electro‐optical properties, processing technologies, and performance.

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Section: Charged Iridium(iii) Complexesmentioning

confidence: 99%

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

et al. 2009

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“…Recently, Janjua et al predicted large second‐order nonlinear optical (NLO) responses of organoimido‐substituted hexamolybdates, where the polyanion served as donor and the covalently bound organoimido residue acted as acceptor (the degree‐of‐charge‐transfer from along the Mo‐N imido bond was found to play a key role in the NLO response) 146. In addition, terpyridines and their transition metal complexes (e.g., with Zn II , Ir III and Ru II ions) were studied in this respect 147. Consequently, the combinations of both in hybrids 20 were also evaluated, as new types of NLO‐active materials (Figure 21b):148 the second‐order NLO response, in particular the static second‐order polarizability along the z ‐axis ( β vec ), of 20 (R = H, β vec = 886.550 × 10 −30 esu), could be enhanced significantly by incorporation of halogen atoms, as additional electron acceptors, in 4/4''‐position of the terpyridine moiety (thereby, β vec gradually increased in the order F < Cl < Br < I).…”

Section: Terpyridines and Inorganic Nanomaterialsmentioning

confidence: 99%

The Marriage of Terpyridines and Inorganic Nanoparticles: Synthetic Aspects, Characterization Techniques, and Potential Applications

et al. 2011

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The utilization of supramolecular chemistry, i.e., metal-to-ligand coordination, in the field of nanotechnology is evaluated with respect to 2,2':6',2″-terpyridine, as tridentate metal binding site. Stabilization as well as directed self-assembly of nanometer-sized materials into ordered arrays are the most widely studied targets of current research. Moreover, energy- and/or electron-transfer processes are enabled when redox-active terpyridine complexes are bound to (semi)conducting species (e.g., fullerenes, polyoxometalates)-thus, applications in nanoelectronics and catalysis are currently arising from these hybrid materials. Progress made in these fields, resulting from the marriage of terpyridines (as well as their metal complexes) and nanostructures, is summarized in this Review Article.

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“…Use of organotransition metal complexes as NLO‐phores permits a combination of properties such as redox or magnetic behavior with desirable optical effects5. Such materials also provide superior chemical, thermal, and mechanical stabilities6, as well as functional flexibility through NLO active electronic charge‐transfer transitions with energies and intensities that are tunable by virtue of the nature, oxidation state, and coordination sphere of the metal center7–17.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and photophysical properties of dicopper(I) metallocyclophanes

Burke¹,

Heirtzler²

2010

Int J of Quantum Chemistry

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Electronic properties have been calculated for derivatives of long lived Cu(I) metallocyclophanes, which are self-assembling coordination complexes that have metal-ligand charge-transfer excited states. The molecules studied here are not the typical linear push-pull type with electron withdrawing and donating substituents at either end. The central C 2 axis is preserved by putting the same type of substituent on one end of the cylindrical molecule. In theory, a pseudo-octupolar species can be obtained by a proper balance of substituents at either end of the cylinder. DFT/PBE0 geometry optimizations of the quinoxaline/pyridine derivatives show a preference for the enantiomeric C 2 isomer over the centrosymmetric C i one. Geometry optimizations of the first excited state using TD-DFT indicate loss of C 2 symmetry and return to the ground state. First order hyperpolarizabilities were calculated using analytic gradients. Gas phase hyperpolarizabilities were enhanced by an order of magnitude when recalculated using a Polarized Continuum Model for the polar solvent acetonitrile. Electron withdrawing groups gave positive total b and donating groups gave negative b, both approximately 400 Â 10 À30 esu. V

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Terpyridine Zn(ii), Ru(iii) and Ir(iii) complexes as new asymmetric chromophores for nonlinear optics: first evidence for a shift from positive to negative value of the quadratic hyperpolarizability of a ligand carrying an electron donor substituent upon coordination to different metal centres

Cited by 56 publications

References 19 publications

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

The Marriage of Terpyridines and Inorganic Nanoparticles: Synthetic Aspects, Characterization Techniques, and Potential Applications

Spectroscopic and photophysical properties of dicopper(I) metallocyclophanes

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