Linkage effects to nonlinear optical properties of porphyrin-appended mixed (porphyrinato)(phthalocyaninato) yttrium(III) double-decker complexes

Third-order nonlinear optical properties of three isomeric tetrapyrrole triads, i.e. mixed (porphyrinato)(phthalocyaninato) yttrium double-decker complexes appended with one metal free porphyrin chromophore at the para, meta, and orthoposition, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit through ester linkage, 3-5, were comparatively investigated along with the model compounds metal free meso-tetrakis(4-tert-butylphenyl) porphyrin H2TBPP (1) and mixed [meso-tetrakis(4-tert-butylphenyl)porphyrinato] [1,4,8,11,15,18,22,25-octakis(butyloxyl)phthalocyaninato] yttrium double-decker complex YIIIH(TBPP) [Pc(α-OC4H9)8] (2) by using Z-scan technique with the fundamental (800 nm) laser emission from a Ti:sapphire femtosecond laser system. Strong reverse saturable absorption (RSA) properties of complexes 2-5 were observed. Interestingly, under highly intense irradiation, an RSA-SA-RSA-SA-RSA switch behavior was evolved in the tight focal intensity regime on the Z-scan profiles of complexes 3-5. Under the laser irradiation with focal intensity of 7.48-8.39 GW.cm-2, the triads 3 and 4 with the metal free porphyrin chromophore appended at the para or meta positions of the meso-phenyl group of the porphyrin ligand in the double-decker unit retained a characteristic response of RSA. In contrast, the triad 5 with the metal free porphyrin chromophore appended at the ortho position has already shown a trend of SA peaks at the same intensity range, revealing the effect of the position of porphyrin-substituent on the nonlinear optical properties of the triads.

[1]  J. Zyss,et al.  Molecular Nonlinear Optics: Materials, Physics, and Devices , 2013 .

[2]  Yong Li,et al.  Investigation of nonlinear optical properties of protonated mixed (porphyrinato)(phthalocyaninato) rare-earth(III) double-decker complexes by Z-scan technique , 2011, Organic Photonics + Electronics.

[3]  Xingzhong Yan,et al.  Mixed (porphyrinato)(phthalocyaninato) rare-earth(III) double-decker complexes for broadband light harvesting organic solar cells , 2011 .

[4]  Xingzhong Yan,et al.  Linkage dependence of intramolecular fluorescence quenching process in porphyrin-appended mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes. , 2010, The journal of physical chemistry. B.

[5]  B. Salih,et al.  Synthesis, Characterization, Electrochemical, and Optic Limiting Properties of Novel CoII, CuII, and Double‐Decker LuIII Phthalocyanines , 2009 .

[6]  B. Salih,et al.  Synthesis, Characterization, Nonlinear Absorption and Electrochromic Properties of Double-Decker Octakis(mercaptopropylisobutyl-POSS)phthalocyaninatolanthanide(III) Complexes , 2008 .

[7]  Fushi Zhang,et al.  Nonlinear optical absorption and refraction properties of ytterbium phthalocyanine dimer and trimer derivative , 2007, SPIE/COS Photonics Asia.

[8]  Werner J. Blau,et al.  Nonlinear Optical Properties of Porphyrins , 2007 .

[9]  James J. Doyle,et al.  A2B2-type push-pull porphyrins as reverse saturable and saturable absorbers. , 2007, Chemical communications.

[10]  S. C. Zilio,et al.  Singlet excited state absorption of porphyrin molecules for pico- and femtosecond optical limiting application , 2006 .

[11]  L. Misoguti,et al.  Nonlinear absorption spectrum of ytterbium bis-phthalocyanine solution measured by white-light continuum Z-scan technique , 2006 .

[12]  Renjie Li,et al.  Controlling the nature of mixed (phthalocyaninato)(porphyrinato) rare-earth(III) double-decker complexes: the effects of nonperipheral alkoxy substitution of the phthalocyanine ligand. , 2006, Chemistry.

[13]  Gong Qi-huang,et al.  Ultrafast third-order optical nonlinearity of several sandwich-type phthalocyaninato and porphyrinato europium complexes , 2005 .

[14]  J. Shirk,et al.  Synthesis of a Bisphthalocyanine and Its Nonlinear Optical Properties , 2005 .

[15]  S. Costa,et al.  Interactions in noncovalent PAMAM/TMPyP systems studied by fluorescence spectroscopy. , 2005, The journal of physical chemistry. B.

[16]  Gema de la Torre,et al.  Role of structural factors in the nonlinear optical properties of phthalocyanines and related compounds. , 2004, Chemical reviews.

[17]  W. Blau,et al.  Nonlinear absorption properties of some 1,4,8,11,15,18,22,25-octaalkylphthalocyanines and their metallated derivatives , 2003 .

[18]  Jayan Thomas,et al.  Nonlinear absorption in certain metal phthalocyanines at resonant and near resonant wavelengths , 2003 .

[19]  V. Nampoori,et al.  Wavelength dependence of nonlinear absorption in a bis-phthalocyanine studied using the Z-scan technique , 2002 .

[20]  P O Hedekvist,et al.  Advanced all-optical logic gates on a spectral bus. , 2001, Applied optics.

[21]  Jayan Thomas,et al.  NONLINEAR ABSORPTION AND OPTICAL LIMITING IN SOLUTIONS OF SOME RARE EARTH SUBSTITUTED PHTHALOCYANINES , 2001 .

[22]  T. Wen,et al.  Substituted tetra-2,3-pyrazinoporphyrazinino copper(II) complexes: synthesis and nonlinear optical refractive and absorptive properties , 1998 .

[23]  Werner J. Blau,et al.  Third-order optical non-linearity in Zn(II) complexes of 5,10,15,20-tetraarylethynyl-substituted porphyrins , 1997 .

[24]  M. Teich,et al.  Fundamentals of Photonics , 1991 .

[25]  Kevin M Smith,et al.  CONCERNING MESO-TETRAPHENYLPORPHYRIN PURIFICATION , 1975 .

[26]  C. C. Wang,et al.  Nonlinear optics. , 1966, Applied optics.

[27]  R. Dhakal,et al.  Organic-inorganic hybrid solar cells made from hyperbranched phthalocyanines , 2011 .

[28]  H. Ünver,et al.  The nonlinear refraction and nonlinear absorption in 4-(4,6-diaminopyrimidin-2-ylthio) substituted double-decker Lu(III) phthalocyanine , 2008 .

[29]  B. Salih,et al.  Synthesis, Characterization and Optical Limiting Properties of Novel Ball-type Four tert-Butylcalix(4)arene Bridged Double-decker Lutetium(III) and Indium(III) Phthalocyanines , 2008 .