Large second-order optical polarizabilities in mixed-valency metal complexes

Laidlaw, W. M.; Denning, R.G.; Verbiest, Thierry; Chauchard, E. A.; Persoons, André

doi:10.1038/363058a0

Cited by 192 publications

(71 citation statements)

References 23 publications

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“…From the survey of existing literature [1][2][3][4][5][6][7], it appears that Cu(II) Schiff bases have been extensively used as biologically active complexes and as catalyst in chemical and the petrochemical industries [8][9][10]. Keeping the above facts in mind, we continue our research work [11] on transition metal complexes with Schiff bases.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and spectroscopic studies of mononuclear mixed ligand Schiff base complexes of Cu(II) involving conjugated heterocyclic nitrogen base and N-phOHA or N-phDHA

Thaker

Surati

Patel

et al. 2006

JICS

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Mononuclear complexes of Cu(II) have been prepared by reacting a 1:1:1 molar ratio of N-phOHA or N-phDHA, dipy or phen and cupric chloride where, N-phOHA = N-phenyl-O-hydroxyacetophenonimine, N-phDHA = N-phenyl-2,4-dihydroxy acetophenonimine, dipy = 2,2′-bipyridil, phen = 1,10-phenanthroline. All complexes were characterized on the basis of their microanalysis data, molar conductance, magnetic moment at room temperature, UV-Vis, IR, 1 H NMR, and ESR spectra. The monomeric and ionic nature of complexes was confirmed by their magnetic moment data and molar conductance values. The ESR spectra of metal chelates in polycrystalline and solution state at 300 K and 77 K were recorded and their silent features are reported. The ESR spectra of the metal chelates provided information about their structure on the basis of Hamiltonian parameters of the complexes and also degree of covalency.

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Section: Introductionmentioning

confidence: 99%

Synthesis and spectroscopic studies of mononuclear mixed ligand Schiff base complexes of Cu(II) involving conjugated heterocyclic nitrogen base and N-phOHA or N-phDHA

Thaker

Surati

Patel

et al. 2006

JICS

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“…The large change of polarizability and hyperpolarizability results in strong NLO effects, [40][41][42][43][44][45][46] then the charge transfer excited state. 41,42 The field dependent excitation energy can be calculated with Eq.…”

Section: Resultsmentioning

confidence: 99%

“…When ΔE BD ＞0, "transition" is off-resonance, superexchange induced, unistep charge transfer, while when, ΔE BD ＜0 it is the resonance coupled, multistep charge-hopping transport. 14 The large change of polarizability and hyperpolarizability can strongly influence the excited state properties of the donor-acceptor dyad or donor-bridgeacceptor triad in the artificial photosynthesis, solar cells and nanoscale devices, which can result in strong nonlinear optical (NLO) effects, [40][41][42][43][44][45][46] then the charge transfer excited state (charge separate excited state on the exciton). 41,42 Theoretically, the excess dipole moment, the polarizability and the first order hyperpolarizability can be fitted by the TD-DFT calculations of the static electric field dependent excitation energy.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Charge Transfer of Carotene‐porphyrin‐fullerene Triad: Sequential or Superexchange Cechanism

Sun

Yue-Hui

et al. 2008

Chin. J. Chem.

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As an excellent artificial photosynthetic reaction center, the carotene (C)-porphyrin (P)-fullerene (F) triad was extensively investigated experimentally. To reveal the mechanism of the intramolecular charge transfer (ICT) on the mimic of photosynthetic solar energy conversion (such as singlet energy transfer between pigments, and photoinduced electron transfer from excited singlet states to give long-lived charge-separated states), the ICT mechanisms of C-P-F triad on the exciton were theoretically studied with quantum chemical methods as well as the 2D and 3D real space analysis approaches. The results of quantum chemical methods reveal that the excited states are the ICT states, since the densities of HOMO are localized in the carotene or porphyrin unit, and the densities of LUMO are localized in the fullerene unit. Furthermore, the excited states should be the intramolecular superexchange charge transfer (ISCT) states for the orbital transition from the HOMO whose densities are localized in the carotene to the LUMO whose densities are localized in the fullerene unit. The 3D charge difference densities can clearly show that some excited states are ISCT excited states, since the electron and hole are resident in the fullerene and carotene units, respectively. From the results of the electron-hole coherence of the 2D transition density matrix, not only 3D results are supported, but also the delocalization size on the exciton can be observed. These phenomena were further interpreted with non-linear optical effect. The large changes of the linear and non-linear polarizabilities on the exciton result in the charge separate states, and if their changes are large enough, the ICT mechanism can become the ISCT on the exciton.

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“…We have also discovered that ruthenium(II) complexes containing 2-phenylimidazo [4,5-f ] [1,10]phenanthroline derivatives show large third-order NLO effects [13][14][15][16][17][18]. However, in contrast to the wealth of studies on quadratic optical nonlinearities of ruthenium complexes [19][20][21][22], their third-order NLO properties have only received limited attention [13][14][15][16][17][18][23][24][25]. In order to further explore this promising field, and also to search for better NLO materials for optical application, we describe here the syntheses, characterization, and third-order NLO properties of four novel ruthenium(II) complexes [Ru(phen) 2 (PNOPH)] 2þ , [Ru(dmp) 2 (PNOPH)] 2þ and their deprotoned complexes (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, PNOPH = 2-(4-nitrophenyl)imidazo- [4,5-f ] [1,10]phenanthroline).The electrochemistry and spectroscopic properties of ruthenium(II) complexes are also presented and discussed.…”

Section: Introductionmentioning

confidence: 85%

Synthesis, characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-(4-nitrophenyl)imidazo[4,5-f] [1,10]phenanthroline

Chao

Yuan

2004

Transition Metal Chemistry

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Two novel Ru II complexes [Ru(phen) 2 (PNOPH)] 2þ and [Ru(dmp) 2 (PNOPH)] 2þ (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, PNOPH = 2-(4-nitrophenyl)imidazo-[4,5-f ][1,10]phenanthroline) and their deprotoned complexes were synthesized and characterized by ES-MS, 1 H-n.m.r, u.v.-vis. and electrochemistry. The crystal structure of the deprotonated complex [Ru(dmp) 2 (PNOP)][ClO 4 ] Á CH 3 CN was determined by means of X-ray single crystal diffraction. Nonlinear optical properties of the Ru II complexes were investigated by Zscan techniques in DMF solution, and all of them exhibited both NLO absorption and self-defocusing effect. The corresponding effective NLO susceptibilities jv 3 j of the complexes are 2.39 Â 10 À12 -5.80 Â 10 À12 esu.

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Large second-order optical polarizabilities in mixed-valency metal complexes

Cited by 192 publications

References 23 publications

Synthesis and spectroscopic studies of mononuclear mixed ligand Schiff base complexes of Cu(II) involving conjugated heterocyclic nitrogen base and N-phOHA or N-phDHA

Synthesis and spectroscopic studies of mononuclear mixed ligand Schiff base complexes of Cu(II) involving conjugated heterocyclic nitrogen base and N-phOHA or N-phDHA

Intramolecular Charge Transfer of Carotene‐porphyrin‐fullerene Triad: Sequential or Superexchange Cechanism

Synthesis, characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-(4-nitrophenyl)imidazo[4,5-f] [1,10]phenanthroline

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