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• W2049251503 abstract "Trimethylsilylation of 1,8-diaminonaphthalene gave 1,8-bis(trimethylsilylamino)naphthalene (1 a), which was in turn lithiated with two molar equivalents of n-butyllithium to give the tris(thf)-solvated dilithium diamide [1,8-{(Me3SiN)Li(thf)}2C10H6](thf) (2 a). Metal exchange of 2 a with TlCl was carried out in two steps, via the previously characterized mixed-metal amide [1-{(Me3SiN)Li(thf)2}-8-{(Me3SiN)Tl}C10H6], to give the dithallium diamide [1,8-{(Me3SiN)Tl}2C10H6] (3 a). Thermolysis of 3 a cleanly gave a 1:1 mixture of the 4,9-bis(trimethylsilylamino)perylenequinone-3,10-bis(trimethylsilylimine) (4 a) and 1 a. By this route, a whole series of silylated homologues of 4 a was obtained in good yields, while the same method proved to be inefficient for the synthesis of the alkyl-substituted analogues. Compound 4 a and its tert-butyldimethylsilyl derivative 4 d were reduced with sodium amalgam to give, after protonation, the corresponding 3,4,9,10-tetraaminoperylenes 7 a and 7 d. Cyclic voltammetry showed two reversible, closely spaced reduction waves (Ered 1=−1.39, Ered 2=−1.59 V versus SCE) corresponding to this conversion. The perylenes 7 a and 7 d are thought to be the primary products in the reaction cascade leading to the perylene derivatives, involving the thermal demetalation of the thallium amides, possibly via TlIITlII intermediates, first to give 7 a and its analogues. The final oxidation of the tetraaminoperylenes by one molar equivalent of 3 a and analogous thallium amides gave the quinoidal derivatives such as 4 a and 4 d, a step that could be studied by direct reaction of the isolated species. The UV/Vis absorption spectra of the 4,9-bis(silylamino)perylenequinone-3,10-bis(silylimines) are characterized by a long-wavelength absorption band with a pronounced vibrational structure (λmax=639 nm, lg ε=4.53) attributed to a π*←π and a π*←n absorption band at 454 nm (lg ε 4.83), along with intense absorption in the UV region. A weak red emission with a rather low quantum yield (Φfl=0.001, λmax=660 nm) is observed upon irradiation of a sample; the lifetime of the emission is only 66 ps. The low emission quantum yield is attributed to the *π←n transition of the amino perylene, which induces strong spin–orbit coupling, leading to a large triplet yield. The triplet state was probed by transient absorption spectroscopy and found to have a lifetime of 200 ns in air, and 1100 ns in argon-flushed solution. Treatment of 4 a with a stoichiometric amount of KF in methanol/water under phase-transfer conditions (with the cryptand [C 222]) gave an almost quantitative yield of the parent compound 4,9-diaminoperylenequinone-3,10-diimine (8). Treatment of 8 with two molar equivalents of the ruthenium complex [Ru(bpy)2(acetone)2](PF6)2, generated in situ, yielded the blue dinuclear ruthenium complex [(bpy)4Ru2{μ2-N,N′:N″,N′′′-[{4,9-(NH2)2-3,10-(NH)2}C20H8]}](PF6)4 (9), the redox properties of which were studied by cyclic voltammetry. The difference in the potentials of the two one-electron redox steps (225 mV) indicates strong coupling of the metal centers through the 4,9-diaminoperylenquinone-3,10-dimine bridging ligand and corresponds to a comproportionation constant Kc of 6.3×103. The UV/Vis absorption spectrum of the mixed valent form, which is stable in air, has a characteristic intervalence charge-transfer (IVCT) band in the near infrared at 930 nm (lg ε=3.95), from which an electronic coupling parameter J of 760 cm−1 could be estimated, placing compound 9 at the borderline between the class II and class III cases in the Robin–Day classification." @default.
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• W2049251503 date "2002-08-16" @default.
• W2049251503 modified "2023-09-23" @default.
• W2049251503 title "Tetraaminoperylenes: Their Efficient Synthesis and Physical Properties" @default.
• W2049251503 doi "https://doi.org/10.1002/1521-3765(20020816)8:16<3732::aid-chem3732>3.0.co;2-5" @default.
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