NDLI: Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Lyubovskaya, Rimma N. Konarev, Dmitri V. Faraonov, Maxim A. Fatalov, Alexey M. Khasanov, Salavat S. Troyanov, Sergey I.
Description	Author Affiliation: Faraonov MA ( Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region 142432, Russia. konarev3@yandex.ru.); Konarev DV ( Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region 142432, Russia. konarev3@yandex.ru.); Fatalov AM ( Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region 142432, Russia. konarev3@yandex.ru and Moscow State University, Leninskie Gory, 119991 Moscow, Russia.); Khasanov SS ( Institute of Solid State Physics RAS, Chernogolovka, Moscow region 142432, Russia.); Troyanov SI ( Moscow State University, Leninskie Gory, 119991 Moscow, Russia.); Lyubovskaya RN ( Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region 142432, Russia. konarev3@yandex.ru.)
Abstract	Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: $(PPN^{+})_{2}\{O=Ti^{IV}(PcCl_{8}^{4−})\}^{2−}$ (1), $(PPN^{+})\{O=Ti^{IV}(Nc˙^{3−})\}˙^{−}·2C_{6}H_{4}Cl_{2}$ (2) and $(PPN^{+})_{2}\{O=Ti^{IV}(AceTPrzPz^{4−})\}^{2−}·1.3C_{6}H_{4}Cl_{2}·0.8C_{6}H_{5}CN$ (3) where $PPN^{+}$ is the bis(triphenylphosphoranylidene)ammonium cation, $PcCl_{8}$ – 2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc – 2,3-naphthalocyanine, AceTPrzPz – tetra(acenaphthenopyrazino)porphyrazine. Salts 1–3 were obtained in the reduction of the parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in o-dichlorobenzene with following precipitation of crystals with n-hexane. Reduction of macrocycles in 1–3 is accompanied by the appearance of intense NIR bands in the solid spectra at 963–1159 nm. It has been found that the extended π-system with linear annulation in $\{O=Ti^{IV}(Nc˙^{3−})\}˙^{−}$ provides the shift of the NIR band to smaller energies (1159 nm) in comparison with those in the spectra of $\{O=Ti^{IV}(Pc˙^{3−})\}˙^{−}$ (995–998 nm). Reduction of macrocycles leads also to the alternation of $C–N_{imine}$ bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with the radical anions in 2. One-dimensional π–π stacking chains and layers are formed in 1 and 3 with diamagnetic $\{O=Ti^{IV}(PcCl_{8}^{4−})\}^{2−}$ and $\{O=Ti^{IV}(AceTPrzPz^{4−})\}^{2−}$ dianions, respectively. Salt 2 contains nearly isolated $[\{O=Ti^{IV}(Nc˙^{3−})\}˙^{−}]_{2}$ dimers with a strong π–π interaction between paramagnetic radical anion macrocycles. As a result, a transition from the triplet to singlet state with antiparallel ordering of spins within the dimers is observed in 2 below 200 K.
ISSN	14779226
Issue Number	11
Journal	Dalton Trans.
Volume Number	46
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2017-03-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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