title: Quantum-chemistry descriptors for photosensitizers based on macrocycles.
abstract: Phthalocyanines, porphyrins, and chlorins have been widely studied as photosensitizers. Both experimental and computational strategies are employed in order to propose new and more active molecules derived from those macrocycles. In this context, there are two main strategies used: (i) the addition of different substituents and (ii) the complexation of the macrocycle with different metallic ions. In this work, we present selected descriptors based on quantum chemistry calculations for forty macrocycles, including some approved drugs. We have found that density functional theory is a suitable methodology to study the large sets of molecules when applying the B3LYP/LanL2DZ methodology for geometry optimization and TD-OLYP/6-31G(d) for absorption spectrum. The inclusion of solvent effects by means of continuum model is important in order to obtain the accurate electronic data. We have verified that by bonding charged or polar substituents to the macrocycle, it is possible to enhance water solvation as well as to improve spectroscopic properties because molecular orbital contributions for Q band can be affected by some substituents. Selected descriptors, electronic and steric, were pointed out as important to propose the new photosensitizers.
authors.affiliation: ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.|Departamento de Química, Instituto Tecnológico da Aeronáutica, São José dos Campos, SP, Brazil.
authors.forename: Fernanda
authors.initials: F
authors.lastname: Bettanin
authors.affiliation: ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.
authors.forename: Felipe C T
authors.initials: FC
authors.lastname: Antonio
authors.affiliation: ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.|Escola de Artes, Ciências e Humanidades, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: Kathia M
authors.initials: KM
authors.lastname: Honorio
authors.affiliation: ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.
authors.forename: Paula
authors.identifier: http://orcid.org/0000-0002-7049-4689
authors.initials: P
authors.lastname: Homem-de-Mello
mesh_terms: D017076:Computer-Aided Design; D015195:Drug Design; D004583:Electrons; D007211:Indoles / Q000737:chemistry; D054833:Isoindoles; D008027:Light; D047028:Macrocyclic Compounds / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D017319:Photosensitizing Agents / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013057:Spectrum Analysis
chemical_list: D007211:Indoles; D054833:Isoindoles; D047028:Macrocyclic Compounds; D017319:Photosensitizing Agents; D011166:Porphyrins; D012997:Solvents; C013647:phthalocyanine
keywords: density functional theory; molecular descriptors; photosensitizers; phthalocyanine; porphyrin