Unusually Strong Long-Distance Metal-Metal Coupling in Bis(ferrocene)-Containing BOPHY: An Introduction to Organometallic BOPHYs.

The first organometallic BOPHY (BOPHY=bis(difluoroboron)-1,2-bis{(pyrrol-2-yl)methylene}hydrazine) containing two ferrocene substituents was prepared through a Knoevenagel condensation between tetramethyl substituted BOPHY and ferrocene carboxaldehyde. An unprecedentedly strong long-range (≈17.2 Å) metal-metal coupling in this new complex was investigated using electrochemical, spectroelectrochemical, and chemical oxidation methods. Electrochemical data is indicative of a 200 mV separation between the first and the second ferrocene-centered oxidation processes. Formation of the mixed-valence states and appearance and disappearance of two NIR bands were observed during stepwise oxidation of the first organometallic BOPHY. The electronic structure and the nature of the excited states in this new chromophore were studied by DFT and TDDFT calculations.

[1]  Kevin Burgess,et al.  BODIPY dyes and their derivatives: syntheses and spectroscopic properties. , 2007, Chemical reviews.

[2]  E. Maligaspe,et al.  Synthesis and charge-transfer dynamics in a ferrocene-containing organoboryl aza-BODIPY donor-acceptor triad with boron as the hub. , 2015, Inorganic chemistry.

[3]  Yun Wei,et al.  Highly fluorescent BF2 complexes of hydrazine-Schiff base linked bispyrrole. , 2014, Organic letters.

[4]  Bart M. J. M. Suijkerbuijk,et al.  Porphyrine mit metallorganischen Gruppen: Synthese und Anwendungen , 2008 .

[5]  M. Venanzi,et al.  Electronic properties of mono-substituted tetraferrocenyl porphyrins in solution and on a gold surface: assessment of the influencing factors for photoelectrochemical applications. , 2015, Chemistry.

[6]  M. Fischer,et al.  Metallfreie organische Farbstoffe für farbstoffsensibilisierte Solarzellen – von Struktur‐Eigenschafts‐Beziehungen zu Designregeln , 2009 .

[7]  Chang-Liang Sun,et al.  Synthesis of mono-(p-dimethylamino)styryl-containing BOPHY dye for a turn-on pH sensor , 2015 .

[8]  André Bessette,et al.  Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices. , 2014, Chemical Society reviews.

[9]  P. Fanwick,et al.  Diruthenium-polyyn-diyl-diruthenium wires: electronic coupling in the long distance regime. , 2014, Journal of the American Chemical Society.

[10]  N. Aratani,et al.  1 Synthetic Strategies Toward Multiporphyrinic Architectures , 2010 .

[11]  A. Heikal,et al.  Photoinduced charge transfer in short-distance ferrocenylsubphthalocyanine dyads. , 2012, Inorganic chemistry.

[12]  V. Nemykin,et al.  Synthesis, characterization, and electron-transfer processes in indium ferrocenyl-containing porphyrins and their fullerene adducts. , 2013, Inorganic chemistry.

[13]  E. Maligaspe,et al.  Redox and photoinduced electron-transfer properties in short distance organoboryl ferrocene-subphthalocyanine dyads. , 2014, Inorganic chemistry.

[14]  M. Fischer,et al.  Metal-free organic dyes for dye-sensitized solar cells: from structure: property relationships to design rules. , 2009, Angewandte Chemie.

[15]  M. S. Gonçalves,et al.  Fluorescent labeling of biomolecules with organic probes. , 2009, Chemical reviews.

[16]  Daoben Zhu,et al.  Electrochromism based on the charge transfer process in a ferrocene–BODIPY molecule , 2009 .

[17]  Gang Qian,et al.  Near-infrared organic compounds and emerging applications. , 2010, Chemistry, an Asian journal.

[18]  N. Kobayashi,et al.  Hydrogenated tetraazaporphyrins--old but new core-modified phthalocyanine analogues. , 2008, Dalton transactions.

[19]  P. Low,et al.  Broad-Band NIR Transient Absorption Spectroscopy of an “All-Carbon”-Bridged Bimetallic Radical Cation Complex , 2015 .

[20]  V. Nemykin,et al.  A new highly fluorescent and symmetric pyrrole-BF2 chromophore: BOPHY. , 2014, Journal of the American Chemical Society.

[21]  E. A. Makarova,et al.  Tuning the near-IR band energy and redox potentials of magnesium tetra(ferrocenyl)tetraazaporphyrins , 2014 .

[22]  C. H. Devillers,et al.  Ferrocene-appended porphyrins: Syntheses and properties , 2009 .

[23]  V. Traven,et al.  NIR-fluorescent coumarin-fused BODIPY dyes with large Stokes shifts. , 2013, Chemical communications.

[24]  B. Suijkerbuijk,et al.  Merging porphyrins with organometallics: synthesis and applications. , 2008, Angewandte Chemie.

[25]  H. Lang,et al.  Spectro)electrochemical investigations on (ferrocenyl)thiophenes modified by tungsten Fischer carbenes , 2014 .

[26]  Andrew C Benniston,et al.  Lighting the way ahead with boron dipyrromethene (Bodipy) dyes. , 2009, Physical chemistry chemical physics : PCCP.

[27]  V. Lynch,et al.  The key role of peripheral substituents in the chemistry of phthalocyanines and their analogs , 2010 .

[28]  Kevin Burgess,et al.  Fluorescent indicators for intracellular pH. , 2010, Chemical reviews.

[29]  A. Harriman,et al.  The chemistry of Bodipy: A new El Dorado for fluorescence tools , 2007 .

[30]  Peter Day,et al.  Mixed Valence Chemistry-A Survey and Classification , 1968 .

[31]  E. A. Makarova,et al.  Energy Transfer from Colloidal Quantum Dots to Near-Infrared-Absorbing Tetraazaporphyrins for Enhanced Light Harvesting , 2015 .

[32]  S. Fukuzumi,et al.  Photoinduced electron transfer in a ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C60 triad. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[33]  H. Lang,et al.  Synthesis and (spectro)electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives. , 2015, Dalton transactions.

[34]  R. Misra,et al.  Ferrocenyl BODIPYs: synthesis, structure and properties , 2012 .

[35]  Jishan Wu,et al.  Far-red and near infrared BODIPY dyes: synthesis and applications for fluorescent pH probes and bio-imaging. , 2014, Organic & biomolecular chemistry.

[36]  Pascal Retailleau,et al.  Synthesis of Highly Functionalized BOPHY Chromophores Displaying Large Stokes Shifts. , 2015, Organic letters.

[37]  E. Maligaspe,et al.  Synthesis, redox properties, and electronic coupling in the diferrocene aza-dipyrromethene and azaBODIPY donor-acceptor dyad with direct ferrocene-α-pyrrole bond. , 2014, Inorganic chemistry.

[38]  A. Harriman,et al.  Boron dipyrrin dyes exhibiting "push-pull-pull" electronic signatures. , 2009, Chemistry.

[39]  F. Miomandre,et al.  Electrochromic and electrofluorochromic properties of a new boron dipyrromethene-ferrocene conjugate , 2013 .

[40]  T. Torres,et al.  Modulating the electronic properties of porphyrinoids: a voyage from the violet to the infrared regions of the electromagnetic spectrum. , 2008, Organic & biomolecular chemistry.

[41]  V. Nemykin,et al.  Long-range metal–metal coupling in transition-metal 5,10,15,20-tetraferrocenylporphyrins , 2011 .

[42]  E. Peña‐Cabrera,et al.  Simple, general, and efficient synthesis of meso-substituted borondipyrromethenes from a single platform. , 2007, Organic letters.

[43]  M. Zandler,et al.  Excitation-wavelength-dependent, ultrafast photoinduced electron transfer in bisferrocene/BF2-chelated-azadipyrromethene/fullerene tetrads. , 2013, Chemistry.

[44]  E. Maligaspe,et al.  Tuning Electronic Structure, Redox, and Photophysical Properties in Asymmetric NIR-Absorbing Organometallic BODIPYs. , 2015, Inorganic chemistry.

[45]  B. Floris,et al.  New developments in chemistry of organometallic porphyrins and their analogs , 2013 .

[46]  C. M. Drain,et al.  Porphyrins as Molecular Electronic Components of Functional Devices. , 2010, Coordination chemistry reviews.

[47]  Anthony Harriman,et al.  Die vielseitige Chemie von Bodipy‐Fluoreszenzfarbstoffen , 2008 .

[48]  Juyoung Yoon,et al.  Recent progress on fluorescent chemosensors for metal ions , 2012 .

[49]  Hong Zheng,et al.  Advances in modifying fluorescein and rhodamine fluorophores as fluorescent chemosensors. , 2013, Chemical communications.

[50]  M. Zandler,et al.  Bisdonor-azaBODIPY-fullerene supramolecules: syntheses, characterization, and light-Induced electron-transfer studies , 2014 .

[51]  M. Zandler,et al.  Syntheses, electrochemistry, and photodynamics of ferrocene-azadipyrromethane donor--acceptor dyads and triads. , 2011, The journal of physical chemistry. A.

[52]  Tebello Nyokong,et al.  Synthetic pathways to water-soluble phthalocyanines and close analogs , 2010 .

[53]  R. Misra,et al.  Heteroatom-Connected Ferrocenyl BODIPYs: Synthesis, Structure, and Properties , 2014 .

[54]  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.

[55]  D. Citterio,et al.  New Trends in Near-Infrared Fluorophores for Bioimaging , 2014, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[56]  J. Rack,et al.  Ultrafast dynamics of a new class of highly fluorescent boron difluoride dyes. , 2015, Physical chemistry chemical physics : PCCP.

[57]  H. Lang,et al.  Influence of P-Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl-Substituted Phospholes. , 2015, Chemistry.

[58]  B. Floris,et al.  Metallocenes meet porphyrinoids: Consequences of a "fusion" , 2015 .

[59]  W. Dehaen,et al.  Fluorescent indicators based on BODIPY. , 2012, Chemical Society reviews.

[60]  N. Kobayashi,et al.  Low symmetry phthalocyanines and their analogues. , 2011, Chemical reviews.

[61]  Barry P Rand,et al.  A 4% Efficient Organic Solar Cell Using a Fluorinated Fused Subphthalocyanine Dimer as an Electron Acceptor , 2011 .

[62]  M. Venanzi,et al.  Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface. , 2012, Chemical communications.

[63]  R. Misra,et al.  Donor-acceptor meso-alkynylated ferrocenyl BODIPYs: synthesis, structure, and properties. , 2013, Dalton transactions.

[64]  Daoben Zhu,et al.  A highly sensitive viscosity probe based on ferrocene-BODIPY dyads. , 2010, Dalton transactions.

[65]  Anthony Harriman,et al.  The chemistry of fluorescent bodipy dyes: versatility unsurpassed. , 2008, Angewandte Chemie.

[66]  Marc Vendrell,et al.  Combinatorial strategies in fluorescent probe development. , 2012, Chemical reviews.

[67]  Neil G. Connelly,et al.  The Electron-Transfer Reactions of Mononuclear Organotransition Metal Complexes , 1984 .

[68]  Zhijian Chen,et al.  Water-soluble BODIPY and aza-BODIPY dyes: synthetic progress and applications , 2014, Frontiers of Chemical Science and Engineering.