Thermodynamics of Supramolecule Formation between Metal Porphyrin and Pyridine Substituted N-Methylpyrrolidinyl-[60]fullerene

Abstract

Thermodynamic characteristics, mechanism, and spectral manifestations of consecutive reactions between (5,10,15,20-tetraphenylporphyrinato)(chloro)indium(III) ((Cl)InTPP) and organic base 2'-(4-pyridyl)-1'-methylpyrrolidinyl-[60]fullerene (PyF) in chloroform were studied using spectrophotometric titration and physicochemical analysis of intermediate forms. The consecutive coordination of two PyF molecules (K 1 = 6.9. 10 4 , K 2 = 9.3. 10 3 l/mol at 298 K) with the formation of (Cl)(PyF)InTPP and (Cl)(PyF) 2 InTPP, and addition of three other PyF molecules on complex periphery producing (Cl)(PyF) 2 InTPP. 3(PyF) (K 3 = 2.3 l 3 /mol 3) were observed at the first, second, and third steps. The third reaction stage most likely corresponds to π-π complex formation equilibrium between the aromatic complex and PyF with a 1:3 stoichiometry. Perspectives for use of PyF-metalloporphyrin complex as a photovoltaic material are considered.

Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

“…The two-step bonding (Figure S7) of four and eight Py 3 F 0 molecules were observed. [99] The quantum-chemical calculation data showed the identical basicity of the 2 0 -(pyridin-4-yl) and 1 0 -(pyridin-3-yl)methyl N atoms (Figure S8).…”

“…The reaction between (Cl)In III TPP and Py was chosen as a model in design of donor-acceptor pairs imitating the primary charge separation in natural photosynthesis. [99] Porphyrins and phthalocyanines proved to be effective electron donors in systems with PET. Fullerene derivatives act most often as electron acceptors due to their unique ability to accumulate electrons with the formation of multianions.…”

“…[101] The research was further continued with substituted both (Cl)InTPP and PyF. [92,99,102] Unsubstituted indium(III) porphyrin and sterically uncomplicated monopyridyl-substituted fullero [60]pyrrolidine were chosen as the most suitable precursors for porphyrin-fullerene dyads (Table S6).…”

“…[ 39 ] Processes of energy and an electron transfer in these systems are initiated from the singlet excited state of the porphyrin sensitizer to the fullerene acceptor, which makes such systems suitable for simulating the primary charge separation during photosynthesis. The first study of donor–acceptor self‐organization in porphyrin–fullerene systems with a highly charged central ion carried out on the example of the axial bonding of 2′‐(pyridin‐4‐yl)‐1′‐methylpyrrolidino[3′,4′:1,2][60]fullerene (PyF) with (Cl)InTPP [ 100 ] where the reaction between (Cl)InTPP and Py was used as a simple model. [ 101 ] The research was further continued with substituted both (Cl)InTPP and PyF.…”

New Donor-Acceptor Porphyrin-Fullerene Dyades

“…[18][19][20][21] Прогресс в синтезе координационных порфирин-фуллереновых супрамолекул явно опережает развитие их физикохимии и поэтому чаще обусловлен хаотическим выбором составов комплексов и методов их сборки или синтеза. Несколько лет назад [22,23] авторы данной статьи, имея богатый опыт в области молекулярного комплексообразования MP с неорганическими и сложными органическими основаниями, [24][25][26][27] приступили к изучению природы, состава и количественных характеристик устойчивости донорно-акцепторных порфирин-фуллереновых комплексов, при образовании которых координационно ненасыщенный MP выступает в качестве акцептора, а пиридильный заместитель в молекуле пирролидинил-[60]фуллерена -в качестве донора электронной плотности. В настоящей работе представлены результаты исследования равновесий и скоростей реакций гидроксооксо (5,10,15,20-…”