Organotransition Metal Complexes for Nonlinear Optics

Morrall, Joseph P.; Dalton, Gulliver T.; Humphrey, Mark G.; Samoć, Marek

doi:10.1016/s0065-3055(07)55002-1

Cited by 138 publications

(89 citation statements)

References 133 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The significant work already published in this area during the last two decades [2][3][4][5][6][7][8][9][10][11] is in agreement with the general understanding that second-order nonlinearities are strongly related to asymmetric push-pull systems, both in organic and organometallic molecular materials. In the case of metallo-organic compounds, the metal centre can be bound to a highly polarizable conjugated backbone, acting hence as an electron releasing or withdrawing group.…”

Section: Introductionsupporting

confidence: 73%

Synthesis and electrochemical studies of η5-monocyclopentadienylruthenium(II) complexes with substituted thiophene nitrile ligands. Crystal structure of [Ru(η5-C5H5)(dppe)(NC{SC4H2}2NO2)][PF6]

Garcia

Mendes

Robalo

et al. 2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Section: Introductionsupporting

confidence: 73%

Synthesis and electrochemical studies of η5-monocyclopentadienylruthenium(II) complexes with substituted thiophene nitrile ligands. Crystal structure of [Ru(η5-C5H5)(dppe)(NC{SC4H2}2NO2)][PF6]

Garcia

Mendes

Robalo

et al. 2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…[1][2][3] In addition, redox-active carbonrich organometallic architectures hold great promise as switchable NLO-active compounds, particularly when the oxidized states are low-lying in energy. [4] One reason is because oxidation of such compounds can "switch on" absorptions at low energy, thus significantly affecting the third-order NLO behavior.…”

Section: Introductionmentioning

confidence: 99%

Multistate Redox‐Active Metalated Triarylamines

et al. 2011

Self Cite

View full text Add to dashboard Cite

International audiencetrans-[(η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(C≡C-4-C6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[₍η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(dppe)2(C≡C-4-C6H4)₃N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe)2] (3) and trans,trans,trans-[₍dppe)2ClRu(C≡C-4-C6H4)₃N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe)2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H4NPh2 and (HC≡C-4-C6H4)3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla-ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches

show abstract

“…In the field of non-linear optics, conjugated unsaturated systems with a transition metal moiety have been employed for their electron delocalization and so-called 'push-pull' characteristics [134,213,214], and the magnetic spin cross-over properties of such carbene-containing molecular wires examined [106,215]. The engineering of designer surfaces functionalized with carbenes [50,51,[216][217][218], and the redox properties and intervalence charge transfer of such organometallic systems on electrode surfaces [219] are other rapidly expanding focus areas.…”

Section: Discussionmentioning

confidence: 99%