Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect.

A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(μ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment.

[1]  Jianlong Xia,et al.  Dithia[3.3]paracyclophane-bridged bimetallic ruthenium acetylide complexes: synthesis, structures and influence of transannular π-π interactions on their electronic properties. , 2013, Dalton transactions.

[2]  Jianlong Xia,et al.  Experimental and theoretical studies of charge delocalization in biruthenium-alkynyl complexes bridged by thiophenes. , 2013, Chemistry, an Asian journal.

[3]  P. Low,et al.  Straightforward Access to Tetrametallic Complexes with a Square Array by Oxidative Dimerization of Organometallic Wires , 2013 .

[4]  H. Lang,et al.  Synthesis and (Spectro)electrochemical Behavior of 2,5-Diferrocenyl-1- phenyl-1 H-phosphole , 2013 .

[5]  Shenghua Liu,et al.  Synthesis, characterization, and electrochemical properties of ferrocenylimidazolium , 2013 .

[6]  P. Fanwick,et al.  Diruthenium Alkynyl Compounds with Phosphonate Capping Groups , 2013 .

[7]  J. Zuo,et al.  New Linear π-Conjugated Diruthenium Compounds Containing Axial Tetrathiafulvalene-acetylide Ligands , 2012 .

[8]  R. Winter,et al.  Ruthenium stilbenyl and diruthenium distyrylethene complexes: aspects of electron delocalization and electrocatalyzed isomerization of the Z-isomer. , 2012, Journal of the American Chemical Society.

[9]  D. C. Graham,et al.  Facile decarboxylation of propiolic acid on a ruthenium center and related chemistry , 2012 .

[10]  M. A. Fox,et al.  Synthesis and Characterization of Dithia[3.3]paracyclophane-Bridged Binuclear Ruthenium Vinyl and Alkynyl Complexes , 2012 .

[11]  P. Beer,et al.  Heteroditopic receptors for ion-pair recognition. , 2012, Angewandte Chemie.

[12]  P. Beer,et al.  Amide and Urea Ferrocene‐Containing Macrocycles Capable of the Electrochemical Sensing of Anions , 2012 .

[13]  Natalie A. Wasio,et al.  Through-bond versus through-space coupling in mixed-valence molecules: observation of electron localization at the single-molecule scale. , 2012, Journal of the American Chemical Society.

[14]  F. Tuna,et al.  Orbital Symmetry Control of Electronic Coupling in a Symmetrical, All-Carbon-Bridged “Mixed Valence” Compound: Synthesis, Spectroscopy, and Electronic Structure of [{Mo(dppe)(η-C7H7)}2(μ-C4)]n+ (n = 0, 1, or 2) , 2012 .

[15]  M. Drescher,et al.  Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states. , 2012, Inorganic chemistry.

[16]  B. le Guennic,et al.  Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands. , 2011, Journal of the American Chemical Society.

[17]  A. Monari,et al.  3,5-Bis(ethynyl)pyridine and 2,6-bis(ethynyl)pyridine spanning two Fe(Cp*)(dppe) units: role of the nitrogen atom on the electronic and magnetic couplings. , 2011, Inorganic chemistry.

[18]  P. Beer,et al.  A 1,2,3,4,5-pentaphenylferrocene-stoppered rotaxane capable of electrochemical anion recognition. , 2011, Chemistry.

[19]  S. Clément,et al.  Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways , 2011 .

[20]  M. DeRosa,et al.  Modulation of electronic couplings within Ru2-polyyne frameworks. , 2011, Journal of the American Chemical Society.

[21]  R. Winter,et al.  Vinyl-ruthenium entities as markers for intramolecular electron transfer processes , 2011 .

[22]  O. Wenger,et al.  Organic mixed valence. , 2011, Chemical reviews.

[23]  D. Yufit,et al.  Spectroscopic and Computational Studies of the Ligand Redox Non-Innocence in Mono- and Binuclear Ruthenium Vinyl Complexes , 2011 .

[24]  M. Drescher,et al.  Fully Delocalized (Ethynyl)(vinyl)phenylene-Bridged Diruthenium Radical Complexes , 2010 .

[25]  Thorfinnur Gunnlaugsson,et al.  Colorimetric and fluorescent anion sensors: an overview of recent developments in the use of 1,8-naphthalimide-based chemosensors. , 2010, Chemical Society reviews.

[26]  D. O′Hare,et al.  Electronic communication through unsaturated hydrocarbon bridges in homobimetallic organometallic complexes. , 2010, Chemical reviews.

[27]  Jianlong Xia,et al.  Bimetallic Ruthenium Complexes: Synthesis, Characterization, and the Effect of Appending Long Carbon Chains to Their Bridges , 2010 .

[28]  J. Zuo,et al.  Linear trimer of diruthenium linked by butadiyn-diyl units: a unique electronic wire. , 2010, Angewandte Chemie.

[29]  A. M. Magill,et al.  Controlled Synthesis of Dinuclear Acetylide-Bridged Ruthenium Complexes , 2010 .

[30]  W. Kaim,et al.  Charge Delocalization in a Heterobimetallic Ferrocene−(Vinyl)Ru(CO)Cl(PiPr3)2 System††Dedicated to Prof. Dr. Helmut Werner on the occasion of his 75th birthday , 2009 .

[31]  Yuya Tanaka,et al.  p-Diethynylbenzene-based molecular wires, Fe–CC-p-C6H2X2–CC–Fe [Fe = Fe(η5-C5Me5)(dppe)]: Synthesis, substituent effects and unexpected formation of benzodifuran complex , 2009 .

[32]  Jianlong Xia,et al.  Synthesis and Characterization of Conjugated Diallenes and Their Binuclear Ruthenium η3-Allyl Complexes , 2009 .

[33]  R. Winter,et al.  Electron transfer across multiple hydrogen bonds: the case of ureapyrimidinedione-substituted vinyl ruthenium and osmium complexes. , 2009, Journal of the American Chemical Society.

[34]  Shenghua Liu,et al.  Synthesis, Characterization, and Substituent Effects of Binuclear Ruthenium Vinyl Complexes [RuCl(CO)(PMe3)3]2(μ-CH═CH−Ar−CH═CH) , 2009 .

[35]  J. Steed Coordination and organometallic compounds as anion receptors and sensors. , 2009, Chemical Society reviews.

[36]  H. Stueger,et al.  Redox-active organometallics: magnetic and electronic couplings through carbon-silicon hybrid molecular connectors. , 2008, Journal of the American Chemical Society.

[37]  Dan Du,et al.  Synthesis and characterization of bimetallic ruthenium complexes connected through linear (CH)(14) chain , 2007 .

[38]  Gareth R. Owen,et al.  sp carbon chains surrounded by sp(3) carbon double helices: coordination-driven self-assembly of wirelike Pt(CC)(n)Pt moieties that are spanned by two P(CH(2))(m)P linkages. , 2007, Journal of the American Chemical Society.

[39]  Li-Yi Zhang,et al.  Wirelike dinuclear ruthenium complexes connected by bis(ethynyl)oligothiophene. , 2007, Inorganic chemistry.

[40]  C. Frisbie,et al.  Temperature and Length Dependence of Charge Transport in Redox-Active Molecular Wires Incorporating Ruthenium(II) Bis(σ-arylacetylide) Complexes , 2007 .

[41]  W. Kaim,et al.  Unconventional mixed-valent complexes of ruthenium and osmium. , 2007, Angewandte Chemie.

[42]  M. Sponsler,et al.  Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes. , 2007, Inorganic chemistry.

[43]  W. Kaim,et al.  Divinylphenylene bridged diruthenium complexes bearing Ru(CO)Cl(PiPr3)2 entities , 2006 .

[44]  F. Barrière,et al.  Use of weakly coordinating anions to develop an integrated approach to the tuning of deltaE(1/2) values by medium effects. , 2006, Journal of the American Chemical Society.

[45]  Zhong-Ning Chen,et al.  Preparation, Characterization, Redox Properties, and UV−Vis−NIR Spectra of Binuclear Ruthenium Complexes [{(Phtpy)(PPh3)2Ru}2{C⋮C−(CHCH)m−C⋮C}]n+ (Phtpy = 4‘-phenyl-2,2‘:6‘,2‘ ‘-terpyridine) , 2006 .

[46]  Anuradha Gupta,et al.  Dependence of field switched ordered arrays of dinuclear mixed-valence complexes on the distance between the redox centers and the size of the counterions. , 2005, Journal of the American Chemical Society.

[47]  M. DeRosa,et al.  Strong electronic couplings between ferrocenyl centers mediated by bis-ethynyl/butadiynyl diruthenium bridges. , 2005, Journal of the American Chemical Society.

[48]  J. Gladysz,et al.  A synthetic breakthrough into an unanticipated stability regime: readily isolable complexes in which C16-C28 polyynediyl chains span two platinum atoms. , 2005, Journal of the American Chemical Society.

[49]  Ian D. Williams,et al.  Synthesis and Characterization of C 10 H 10 -Bridged Bimetallic Ruthenium Complexes , 2005 .

[50]  Laura Orian,et al.  Electronic communication in heterobinuclear organometallic complexes through unsaturated hydrocarbon bridges , 2004 .

[51]  W. M. Leevy,et al.  Crown ethers: sensors for ions and molecular scaffolds for materials and biological models. , 2004, Chemical reviews.

[52]  J. Launay,et al.  Molecular wires built from binuclear cyclometalated complexes. , 2003, Journal of the American Chemical Society.

[53]  H. Xia,et al.  Synthesis and Characterization of Bimetallic Ruthenium Complexes with (CH)6 and Related Bridges , 2003 .

[54]  R. Friend,et al.  Synthesis and optical characterisation of platinum(ii) poly-yne polymers incorporating substituted 1,4-diethynylbenzene derivatives and an investigation of the intermolecular interactions in the diethynylbenzene molecular precursorsElectronic supplementary information (ESI) available: atomic cooordi , 2003 .

[55]  M. F. Lo,et al.  Synthesis and characterization of linear (CH)8-bridged bimetallic ruthenium complexes , 2002 .

[56]  T. Swager,et al.  Conjugated polymers containing 2,3-dialkoxybenzene and iptycene building blocks. , 2001, Organic letters.

[57]  J. Tour,et al.  Accoutrements of a molecular computer: switches, memory components and alligator clips , 2001 .

[58]  J. Steed First- and second-sphere coordination chemistry of alkali metal crown ether complexes , 2001 .

[59]  Philip A. Gale,et al.  Anion Recognition and Sensing: The State of the Art and Future Perspectives. , 2001, Angewandte Chemie.

[60]  P. Low,et al.  Oxidation chemistry of metal-bonded C4 chains: A combined chemical, spectroelectrochemical, and computational study , 2000 .

[61]  Frédéric Paul,et al.  Organometallic molecular wires and other nanoscale-sized devices: An approach using the organoiron (dppe)Cp*Fe building block , 1998 .

[62]  N. Krause,et al.  Improved Procedures for the Palladium-Catalyzed Coupling of Terminal Alkynes with Aryl Bromides (Sonogashira Coupling)† , 1998 .

[63]  E. Solomon,et al.  Detailed spectroscopic analysis of half-met hemocyanins: mixed-valent contributions to electronic properties and structure , 1989 .

[64]  D. Richardson,et al.  Determination of E20-E10 in multistep charge transfer by stationary-electrode pulse and cyclic voltammetry: application to binuclear ruthenium ammines , 1981 .

[65]  Charles J. Pedersen,et al.  Cyclic polyethers and their complexes with metal salts , 1967 .