Synthesis and Nonlinear Optical Properties of Fluorine‐Containing Naphthalocyanines

Abstract

The fluorine-containing metal naphthalocyanines [F16NcGaCl] (7) and [(F16NcGa)2O] (8), which represent the first examples of peripherally fluorine substituted naphthalocyanines, were synthesized, and the nonlinear optical transmission was studied. Peripheral substitution by fluorine atoms enhances the solubility and photostability of the naphthalocyanines. In particular, for the axially mu-oxo-bridged naphthalocyanine dimer 8, practically no aggregation was observed in organic solvents and it has proved to be an efficient optical limiter when irradiated with laser light pulses at the wavelength of 532 nm, with pulse duration of 5 ns and repetition rate of 20 Hz.

Synthesis and strong optical limiting response of graphite oxide covalently functionalized with gallium phthalocyanine

“…A high architectural flexibility in a Pc structure facilitates the tailoring of their physical, optoelectronic and chemical parameters in a very broad range [1][2][3][4][5][6]. The exploitation of the chemical reactivity of the Ga-Cl bond in the R x PcGaCl (R: peripheral substituents in the Pc macrocycle) can allow the preparation of a series of highly soluble axially substituted and bridged Pc complexes [7][8][9][10][11][12][13][14]. Axial substituents in Pcs influence favorably nonlinear optical (NLO) absorption for the presence of a dipole moment perpendicular to the macrocycle in the axially substituted phthalocyanines [15][16][17][18][19][20][21].…”

Synthesis and high ranked NLT properties of new sulfonamide-substituted indium phthalocyanines

“…5). In the case of 9, F lim is comparable to that of other indium phthalo-and naphthalocyanines with axial halogens [26][27][28][29][30][31][32][33][34][35][36][37][38]. In the case of complex 7, the limiting threshold could not be exactly determined within the experimental range of incident fluences.…”

“…Electron-withdrawing substituents are known to produce an enhancement on the NLT properties of phthalocyanines [35,36]. Taking this in consideration, we idealized the synthesis of three phthalocyanine derivatives bearing eight sulfonamide groups.…”

“…When excited-state absorption occurs from a triplet excited state the related OL effect can be further improved in Pcs through the coordination of heavy central atoms, e.g. Pb [25] or In [26][27][28][29][30][31][32][33][34][35][36][37][38], which accelerate intersystem crossing (ISC) by means of spin-orbit coupling in the excited complex.…”

Novel phthalocyanines with naphthalenic substituents

“…As bulky electron rich units, the presence of naphthalenyl groups on the periphery of phthalocyanines modifies the electronic spectra both in solution and in the solid state. Naphthalocyanines are an intensely investigated subgroup of phthalocyanines in which naphthalene moieties are attached to the four pyrrole units of the porphyrazine core [21]. Although naphthalocyanines have been frequently reported, phthalocyanines with naphthalenyl substituents are relatively less studied and only a few well-characterized examples are available.…”