159276-98-9

Upstream product

• 123931-99-7 bis[1,2-bis(diphenylphosphine)ethane]ruthenium dichloride 

Downstream Products

• 199533-73-8 [(DPPE)((C₆H₅)2P(CH₂)2P(C₆H₅)(C₆H₄))Ru](PF₆) 

Relevant academic research and scientific papers

Novel carbon-rich binuclear ruthenium complexes with bis(allenylidene) bridges

Diruthenium(II) complexes with new bis(η1-allenylidene) bridges are produced by double activation of molecules containing two prop-2-yn-1-ol groups and offer two reversible redox processes.

Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex

The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-ξC-1-C6H2-3,5-Et2-4-ξCC6H4-4-ξCH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-ξC-1-C6H2-3,5-Et2-4-ξCC6H4-4-ξC-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-ξC-1-C6H2-3,5-Et2-4-ξCH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit. Electrochemical studies reveal two (5) or one (6-10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π-π transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6-10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption.

Syntheses, Electrochemical, Linear Optical, and Cubic Nonlinear Optical Properties of Ruthenium-Alkynyl-Functionalized Oligo(phenylenevinylene) Stars

The syntheses of trans-[Ru(C≡CC6H4-4-CHO)(C≡CC6H4-4-R)(dppe)2] (R=H (9a), NO2 (9b), CHO (9c), C≡CC6H3-3,5-Et2 (9d), (E)-CHCHC6H4-4-tBu (9e); dppe=1,2-bis(diphenylphosphino)ethane), trans-[Ru(C≡CC6H4-4-R)Cl(dppe)2] (R=C≡CC6H3-3,5-Et2 (11a), (E)-CHCHC6H4-4-tBu (11b), (E)-CHCHC6H4-4-NO2 (11c)), 1,2,4,5-{trans-[(dppe)2(RC6H4C≡C)Ru{C≡CC6H4-4-(E)-CHCH}]}4C6H2 (R=H (14a), C≡CC6H3-3,5-Et2 (14b), (E)-CHCHC6H4-4-tBu (14c)), 1-I-3,5-{trans-[(L2)2(R)Ru{C≡CC6H4-4-(E)-CHCH}]}2C6H3 (L2=1,1-bis(diphenylphosphino)methane (dppm)), R=Cl (15a); L2=dppe, R=C≡CPh (15b), R=C≡CC6H4-4-NO2 (15c)), 1-Me3SiC≡C-3,5-{trans-[(L2)2(R)Ru{C≡CC6H4-4-(E)-CHCH}]}2C6H3 (L2=dppm, R=Cl (16a); L2=dppe, R=C≡CPh (16b)), 1-HC≡C-3,5-{trans-[(dppe)2(R)Ru{C≡CC6H4-4-(E)-CHCH}]}2C6H3 (R=Cl (17a), R=C≡CPh (17b)), and 1,3,5-{trans-[(dppe)2(3,5-R2-C6H3C≡C)Ru{C≡CC6H4-4-(E)-CHCH}]}3C6H3 (R=(E)-CHCHC6H4-4-C≡C-trans-[Ru(C≡CPh)(dppe)2] (18)) are reported together with those of the precursor alkynes 1-RC≡C-3,5-Et2C6H3 (R=SiMe3 (2), H (3), C6H4-4-C≡CSiMe3 (5), C6H4-4-C≡CH (6)). The identities of 9c, 9d, 9e, 11a, and trans-[Ru{C≡CC6H4-4-(E)-CHCHC6H4-4-tBu}2(dppe)2] (12 and 12′) were confirmed by single-crystal X-ray diffraction studies. The electrochemical properties of 9a-e, 11a-b, 14a-c, 15a-c, 16b, 17a, 17b, and 18 were assessed by cyclic voltammetry; the studies reveal that potentials for the fully/quasi-reversible metal-centered oxidation processes decrease upon introduction of solubilizing alkyl substituents and increase upon increasing acceptor substituent strength; other structural variations have little impact. UV/Vis-NIR spectroscopic studies on these complexes reveal lowest-energy metal-ligand charge transfer (MLCT) bands that redshift upon increasing the acceptor substituent strength, blueshift on alkyl incorporation, and gain in intensity on progression from linear to star complexes. Low-temperature UV/Vis-NIR spectroelectrochemical studies of 14a-c show the appearance of an intense low-energy band at 7400-7900cm-1 that is redshifted upon π-system lengthening and alkyl substituent incorporation. The cubic nonlinear optical properties of 9d, 9e, 14a-c, 15a-c, 16b, 17a,b, and 18 were assayed by femtosecond Z-scan studies at benchmark wavelengths (750 and 800nm) in the near-IR region, with nonlinearity increasing upon nitro incorporation; the values for the E-ene-linked dendrimers in these studies are much larger than yne-linked analogues. Compounds 9d, 9e, 14a-c, and 18 were further examined by broad-spectral-range femtosecond Z-scan studies; the cruciform complexes have appreciable multiphoton absorption cross-sections, with maximal values close to two and three times the wavelength of the linear optical absorption maxima. Super stars: (4-Formylphenylethynyl)ruthenium complexes (see figure) are shown to undergo "chemistry-on-complex" Horner-Wadsworth-Emmons coupling to afford a range of tri- and tetraruthenium-functionalized star molecules and a nonaruthenium dendrimer. The products are nonlinear optical (NLO)-active, with linear optical properties that are redox-switchable.