93 (s, 4H, 22% yield). 1 H NMR (400 MHz ppm): 9.01 (d, 2H, 3 J HH = 4.8 Hz 3H, 3 J HH = 7.2 Hz, H fluorenyl, H 5 ), 7.97 (d, 2H, 3 J HH = 8.0 Hz, H phenylene ), 7.71 (m, 11H, H fluorenyl, H 8 and ortho H PPh ) meta H PPh ), 7.03 (m, 10H, 3 J HH ~ 7.6 Hz, meta H PPh and H phenylene ), 4.22 (s, 4H, 2CH 2-fluorenyl ), 4.21 (s, 2H, 1CH 2-fluorenyl ) ppm) : 50.0 (s). MS (ESI in CH 2 Cl 2 /CH 3 CN): calcd for C 119 H 89 ClN 4 P 4 Ru: 1835.4 [MH] + , found 1835, pp.41281779-128 ,
Elemental Analysis: calcd for C 119 H 89 ClN 4 P 4 Ru : C, 77, 10 -3 M -1 .cm -1 ), CH 2 Cl 2 FT-IR (KBr disc, pp.263-423, 1835. ,
trifluorenyl)-20-(4-ethynyl-ruthenium-phenyl) porphyrinato 4 -In a Schlenk tube, mmol) and [Ru(dppe, p.15 ,
The mixture was monitored by 31 P and 1 H NMR spectroscopy, and the reaction was complete in 72 hours. The solution was concentrated under reduced pressure and adding ether gave the desired vinylidene as the precipitated solid. The unreacted ruthenium salt remained in ether. The precipitate was filtered, dissolved in 10 mL of DCM and triethylamine (0.25 mL) was added dropwise to the solution. The brown green solution was then concentrated and passed through a short basic alumina column using DCM and 2% triethylamine as eluent. The solution was concentrated and addition of ether gave a greenish brown precipitate which was filtered and identified as 4. (19 mg, 25% yield). 1 H NMR (400 MHz, distilled dichloromethane (DCM, 20 mL) was stirred under argon 9.03 (s, 4H, H ?-pyrrolic ), 8.41 (m, 3H, H fluorenyl, H 1 ), 8.28 (m, 3H, H fluorenyl, pp.7-53 ,
6 Hz, meta H PPh and H phenylene ), 4.22 (s, 4H, 2CH 2-fluorenyl ), 4.21 (s, 2H, 1CH 2-fluorenyl ), 2.80 (m, 8H, HH ~ 7.6 Hzpara PPh), 129.0 (para PPh) ppm): 49.7 (s). MS (ESI in CH 2 Cl 2 /CH 3 CN): calcd for C 119 H 87 ClN 4 P 4 ZnRu: 1898.3923 [M] + , found: 1898.3932 [M] + . Elemental analysis: calcd References, pp.31-81 ,
Ferrocene-appended porphyrins: Syntheses and properties, Coordination Chemistry Reviews, vol.253, issue.1-2, pp.21-36, 2009. ,
DOI : 10.1016/j.ccr.2007.11.025
Group 8 metal alkynyl complexes for nonlinear optics, Journal of Organometallic Chemistry, vol.751, pp.181-200, 2014. ,
DOI : 10.1016/j.jorganchem.2013.10.008
URL : https://hal.archives-ouvertes.fr/hal-00929871
Enhanced two-photon absorption cross-sections of zinc(II) tetraphenylporphyrins peripherally substituted with d6-metal alkynyl complexes, New Journal of Chemistry, vol.32, issue.180, pp.2192-2195, 2012. ,
DOI : 10.1039/c2nj40589j
URL : https://hal.archives-ouvertes.fr/hal-00855371
-Zinc(II) Ferrocenylporphyrin Based Fluorescence Switches, Inorganic Chemistry, vol.46, issue.18, pp.7247-7249, 2007. ,
DOI : 10.1021/ic0703326
URL : https://hal.archives-ouvertes.fr/in2p3-00315956
Metal alkynyl complexes as switchable NLO systems, Coordination Chemistry Reviews, vol.255, issue.21-22, pp.2530-2541, 2011. ,
DOI : 10.1016/j.ccr.2011.02.021
URL : http://hdl.handle.net/1885/68064
Linear porphyrin dimers with fluorenyl arms linked by an ethynyl bridge, Tetrahedron, vol.69, issue.34, pp.7112-7124, 2013. ,
DOI : 10.1016/j.tet.2013.06.019
URL : https://hal.archives-ouvertes.fr/hal-00840579
Fluorenyl dendrimer porphyrins: synthesis and photophysical properties, Tetrahedron, vol.65, issue.51, pp.10693-10700, 2009. ,
DOI : 10.1016/j.tet.2009.10.043
Photophysical properties of porphyrins, phthalocyanines, and benzochlorins, Inorganica Chimica Acta, vol.279, issue.2, pp.226-231, 1998. ,
DOI : 10.1016/S0020-1693(98)00137-6
Electroactive films of poly(tetraphenylporphyrins) with reduced bandgap, Journal of Electroanalytical Chemistry, vol.597, issue.1, pp.19-27, 2006. ,
DOI : 10.1016/j.jelechem.2006.07.039
URL : https://hal.archives-ouvertes.fr/hal-00176728
Selective anodic preparation of 1D or 2D electroactive deposits from 5,15-bis-(9H-fluoren-2-yl)-10,20-diphenyl porphyrins, Journal of Electroanalytical Chemistry, vol.606, issue.2, pp.103-116, 2007. ,
DOI : 10.1016/j.jelechem.2007.06.003
URL : https://hal.archives-ouvertes.fr/hal-00355413
A simple synthesis of trans-RuCl(CCR)(dppe)2 complexes and representative molecular structures, Journal of Organometallic Chemistry, vol.694, issue.15, pp.2350-2358, 2009. ,
DOI : 10.1016/j.jorganchem.2009.03.033
Covalent Attachment of Porphyrins and Ferrocenes to Electrode Surfaces through Direct Anodic Oxidation of Terminal Ethynyl Groups, Angewandte Chemie International Edition, vol.42, issue.49, pp.12897-12900, 2013. ,
DOI : 10.1002/anie.201307453
Electrochromic Linear and Nonlinear Optical Properties of Alkynylbis(diphosphine)ruthenium Complexes, Journal of the American Chemical Society, vol.125, issue.2, pp.602-610, 2003. ,
DOI : 10.1021/ja0277125
): Misleading Aspects of the ESR Anisotropy, Organometallics, vol.28, issue.7, pp.2253-2266, 2009. ,
DOI : 10.1021/om801138q
Electrochemical and spectroelectrochemical characterization of meso-tetra-alkyl porphyrins, Electrochimica Acta, vol.50, issue.12, pp.2445-2451, 2005. ,
DOI : 10.1016/j.electacta.2004.10.070
.pi.-Cation radicals and dications of metalloporphyrins, Journal of the American Chemical Society, vol.92, issue.11, pp.3451-3459, 1970. ,
DOI : 10.1021/ja00714a038
Noninnocent Ligand Behavior in Diruthenium Complexes Containing a 1,3-Diethynylbenzene Bridge, Organometallics, vol.28, issue.17, pp.5266-5269, 2009. ,
DOI : 10.1021/om900200n
Substituted group and side chain effects for the porphyrin and zinc(II)???porphyrin derivatives: A DFT and TD-DFT study, Journal of Luminescence, vol.142, pp.8-16, 2013. ,
DOI : 10.1016/j.jlumin.2013.03.037
Experimental and Theoretical Studies on Organic D-??-A Systems Containing Three-Coordinate Boron Moieties as both ??-Donor and ??-Acceptor, Chemistry - A European Journal, vol.64, issue.89, pp.1369-1382, 2012. ,
DOI : 10.1002/chem.201102059
Spectroscopy of Free-Base N-Confused Tetraphenylporphyrin Radical Anion and Radical Cation, The Journal of Physical Chemistry A, vol.115, issue.24, pp.6456-6471, 2011. ,
DOI : 10.1021/jp200411q
Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp???]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp???=Cp; L2=dppe; Cp???=Cp???), Journal of Organometallic Chemistry, vol.692, issue.15, pp.3277-3290, 2007. ,
DOI : 10.1016/j.jorganchem.2007.03.042
Simple construction of an infrared optically transparent thin-layer electrochemical cell, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, vol.317, issue.1-2, pp.179-187, 1991. ,
DOI : 10.1016/0022-0728(91)85012-E
Density-Functional Theory for Time-Dependent Systems, Physical Review Letters, vol.52, issue.12, pp.997-1000, 1984. ,
DOI : 10.1103/PhysRevLett.52.997
A new hybrid exchange???correlation functional using the Coulomb-attenuating method (CAM-B3LYP), Chemical Physics Letters, vol.393, issue.1-3, pp.51-57, 2004. ,
DOI : 10.1016/j.cplett.2004.06.011
On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules, Dalton Trans., vol.29, issue.89, pp.3347-3363, 2014. ,
DOI : 10.1039/C3DT52836G
cclib: A library for package-independent computational chemistry algorithms, Journal of Computational Chemistry, vol.46, issue.5, pp.839-845, 2008. ,
DOI : 10.1002/jcc.20823