Квантово-химическое моделирование оптических и физико-химических свойств дифильных спиропиранов

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Abstract

Метод TD-DFT впервые применен для расчета электронных переходов дифильных спиросоединений. Показано, что он дает принципиально верное распределение электронной плотности, соответствующее результатам, полученным с помощью метода CASSCF, и позволяет предсказать природу электронного перехода мероцианиновой формы. Для отрицательных фотохромов обнаружена возможность существования конических пересечений поверхностей потенциальной энергии основного и возбужденного электронных состояний, что может являться причиной замедленного фотохромизма данных соединений. Показана принципиальная возможность использования TD-DFT для предсказания оптических характеристик длинноцепочечных спиропиранов при условии использования шкалирующих регрессий. Впервые разработаны линейные регрессии для таких соединений, учитывающие набор физических параметров растворителя в явном виде. Это позволило получить унифицированную эмпирическую корректировку, учитывающую сольватохромный эффект. Полученные результаты могут быть использованы в качестве основы для разработки базового концепта, учитывающего влияние растворителя на спектральные свойства спиросоединений, и построения единой регрессионной модели, охватывающей различные проявления сольвато- и фотохромизма.

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About the authors

Ю. М. Селивантьев

РХТУ им. Д.И. Менделеева; ИФХЭ РАН

Email: raitman.o.a@muctr.ru
Russian Federation, Москва, Миусская пл. 9; Москва, Ленинский просп., 31, к. 4

А. Н. Морозов

РХТУ им. Д.И. Менделеева

Email: raitman.o.a@muctr.ru
Russian Federation, Москва, Миусская пл. 9

Н. Л. Зайченко

ФИЦ ХФ РАН

Email: raitman.o.a@muctr.ru
Russian Federation, Москва, ул. Косыгина, 4

А. В. Любимов

ФИЦ ХФ РАН

Email: raitman.o.a@muctr.ru
Russian Federation, Москва, ул. Косыгина, 4

О. А. Райтман

ИФХЭ РАН

Author for correspondence.
Email: raitman.o.a@muctr.ru
Russian Federation, Москва, Ленинский просп., 31, к. 4

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Supplementary files

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2. Fig. 1. Scheme of the opening of the pyran ring and the structure of the studied compounds.

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3. Fig. 2. Theoretically possible conformational isomers of 1'-hexadecyl-3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indoline] Ι.

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4. Fig. 3. Experimental absorption spectra of 1'-hexadecyl-3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indoline] (I) in organic solvents.

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5. Fig. 4. CASSCF(14,14,5)/cc-pVTZ (91–104) active space orbitals and frontier orbitals calculated by the DFT/def2-TZVP method for 1'-hexadecyl-3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indoline] (Ι).

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6. Fig. 5. Frontier orbitals (DFT/def2-TZVP/TTC/acetonitrile) for compounds II and III.

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7. Fig. 6. a) Structure II (TTC) at the minimum with the dihedral angle N(54) – C. 62) – C. 24) – C. 22) of 85°; b) potential energy surfaces of the ground and first excited states during rotation around the C. 62) –C(24) bond. Relative energies along the ordinate axis are given in kJ/mol.

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8. Fig. 7. (a) The structure of the TTC conformation of compound III; b) experimental absorption spectra of the initial 10–4 M solution of III in acetonitrile (red), after adding 1 equiv HCl (blue); after adding 1 equiv NaOH (green); calculated λmax value (dotted line)

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