Controlling J-Aggregates Formation and Chirality Induction through Demetallation of a Zinc(II) Water Soluble Porphyrin

International Journal of Molecular Sciences

Maria Angela Castriciano¹  Mariachiara Trapani¹  Roberto Zagami¹  Robert F. Pasternack²  Ilaria Giuseppina Occhiuto³  LuigiMonsù Scolaro³  Andrea Romeo³ 

[1] CNR - ISMN Istituto per lo Studio dei Materiali Nanostrutturati c/o Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, V.le F. Stagno D’Alcontres, 31-98166 Messina, Italy;Department of Chemistry, Swarthmore College, 500 College Avenue, Swarthmore, PA 19081, USA;Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina and C.I.R.C.M.S.B V.le F. Stagno D’Alcontres, 31-98166 Messina, Italy;

关键词: J-aggregates;    symmetry breaking;    demetallation kinetics;    aggregation kinetics;    chiral supramolecular assemblies;   

DOI  :  10.3390/ijms21114001

来源: DOAJ

【 摘 要 】

Under acidic conditions and at high ionic strength, the zinc cation is removed from its metal complex with 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS₄) thus leading to the diacid free porphyrin, that subsequently self-organize into J-aggregates. The kinetics of the demetallation step and the successive supramolecular assembly formation have been investigated as a function of pH and ionic strength (controlled by adding ZnSO₄). The demetallation kinetics obey to a rate law that is first order in [ZnTPPS₄] and second order in [H⁺], according to literature, with k₂ = 5.5 ± 0.4 M⁻² s⁻¹ at 298 K (IS = 0.6 M, ZnSO₄). The aggregation process has been modeled according to an autocatalytic growth, where after the formation of a starting seed containing m porphyrin units, the rate evolves as a power of time. A complete analysis of the extinction time traces at various wavelengths allows extraction of the relevant kinetic parameters, showing that a trimer or tetramer should be involved in the rate-determining step of the aggregation. The extinction spectra of the J-aggregates evidence quite broad bands, suggesting an electronic coupling mechanism different to the usual Frenkel exciton coupling. Resonance light scattering intensity in the aggregated samples increases with increasing both [H⁺] and [ZnSO₄]. Symmetry breaking occurs in these samples and the J-aggregates show circular dichroism spectra with unusual bands. The asymmetry g-factor decreases in its absolute value with increasing the catalytic rate k_c, nulling and eventually switching the Cotton effect from negative to positive. Some inferences on the role exerted by zinc cations on the kinetics and structural features of these nanostructures have been discussed.

【 授权许可】

Unknown