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首页> 外文期刊>Chemistry: A European journal >Tetraaminoperylenes: Their Efficient Synthesis and Physical Properties
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Tetraaminoperylenes: Their Efficient Synthesis and Physical Properties

机译：四氨基per：它们的高效合成和物理性质

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摘要

Trimethylsilylation of 1,8-diaminonaphthalene gave 1,8-bis(trimethylsilylamino)naphthalene (1a), which in turn lithiated with two molar equivalents of n-butyllithium to give the tris(thf)-solvated dilithium diamide [1,8-{(Me_3SiN)Li(thf)}_2C_10H_6](thf) (2a). Metal exchange of 2a with TlCl was carried out in two steps, via the previously characterized mixed-metal amide [1-{(Me_3SiN)Li(thf)_2}-8-{(Me_3SiN)Tl}C_10H_6],to give the dithallum diamide [1,8-{(Me_3SiN)Tl}_2C_10H_6] (3a). Thermolysis of 3a cleanly gave a 1:1 mixture of the 4,9-bis(trimethylsilylamino)perylenequinone-3,10-bis(trimethylsilylimine) (4a) and 1a. By this route, a whole series of silylated homologues of 4a was obtained in good yields, while the same method proved to be inefficient for the synthesis of the alkyl-substituted analogues. Compound 4a and its tert-butyldimethylsilyl derivative 4d were reduced with sodium amalgam to give, after protonation, the corresponding 3,4,9,10-tetraaminoperylenes 7a and 7d. Cyclic voltammetry showed two reversible, closely spaced reduction waves (E_red 1 = - 1.39, E_red 2 = -1.59 V versus SCE) corresponding to this conversion. The perylenes 7a and 7d are though to be the primary products in the reaction cascade leading to the perylene derivatives, involving the thermal demetalation of the thallium amides, possibly via Tl~(II)-Tl~(III) intermediates, first to give 7a and its analogues. The final oxidation of the tetraaminoperylenes by one molar equivalent of 3a and analogous thallium amides gave the quinoidal derivatives such as 4a and 4d, 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 (lambda_max = 639 nm, lg epsilon = 4.53) attributed to a pi~* <- pi and a pi~* < - n absorption band at 454 nm (lg epsilon 4.83), along with intense absorption in the UV region. A weak red emission with a rather low quantum yield (PHI_fl = 0.001, lambda_max = 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 ~*pi < - 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 4a 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[(PF_6)_2, generated in situ, yielded the bule dinuclear rutenium complex [(bpy)_4Ru_2{mu_2-N,N':N",N'"-[{4,9-(NH_2)_2-3,10-(NH)_2}C_20H_8]}](PF_6_4 (9), the redox properties of which were studied by cyclic voltammetry. The difference in the voltammetry. The difference in the potentials of the two one-electron redox steps (225 mV) indicates strong coupling of the metal centers strong coupling of the metal centers through the 4,9-diaminoperylenquinone-3,10-dimine bridging ligand and corresponds to a comproportionation constant K_c of 6.3 X 10~3. 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 infared at 930 nm (lg epsilon = 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.
机译：1,8-二氨基萘的三甲基甲硅烷基化反应得到1,8-双（三甲基甲硅烷基氨基）萘（1a），依次用2摩尔当量的正丁基锂锂化，得到三（thf）溶剂化的二酰胺二锂[1,8- { （Me_3SiN）Li（thf）} _ 2C_10H_6]（thf）（2a）。通过先前表征的混合金属酰胺[1-{（Me_3SiN）Li（thf）_2} -8-{（Me_3SiN）Tl} C_10H_6]分两步进行2a与TlCl的金属交换，得到对苯二酚二酰胺[1,8-{（Me_3SiN）Tl} _2C_10H_6]（3a）。干净地热解3a，得到4,9-双（三甲基甲硅烷基氨基）per醌-3,10-双（三甲基甲硅烷基limine）（4a）和1a的1：1混合物。通过这种途径，以高收率获得了一系列的4a甲硅烷基化的同源物，而事实证明，该方法对于合成烷基取代的类似物是无效的。用汞齐钠将化合物4a及其叔丁基二甲基甲硅烷基衍生物4d还原，在质子化后得到相应的3,4,9,10-四氨基per7a和7d。循环伏安法显示了与该转换相对应的两个可逆的，紧密间隔的还原波（E_red 1 =-1.39，E_red 2 = -1.59 V vs SCE）。 per 7a和7d虽是反应级联反应中的主要产物，但会导致derivatives衍生物发生，化反应，涉及酰胺的热脱金属反应，可能会通过Tl〜（II）-Tl〜（III）中间体首先生成7a。及其类似物。一摩尔当量的3a和类似的th酰胺对四氨基per的最终氧化，得到醌型衍生物，例如4a和4d，该步骤可以通过分离的物质的直接反应来研究。 4,9-双（甲硅烷基氨基）per醌-3,10-双（甲硅酰亚胺）的UV / Vis吸收光谱的特征在于具有明显振动结构的长波吸收带（lambda_max = 639 nm，lg epsilon = 4.53） ）归因于pi〜* <-pi和pi〜* <-n在454 nm的吸收带（lg epsilon 4.83），以及在UV区的强烈吸收。样品照射后，观察到微弱的红色发射，量子产率较低（PHI_fl = 0.001，lambda_max = 660 nm）;发射的寿命仅为66 ps。低发射量子产率归因于氨基per的〜* pi <-n跃迁，该跃迁诱导了强烈的自旋轨道耦合，从而导致了较大的三重态产率。通过瞬态吸收光谱对三重态进行了探测，发现其在空气中的寿命为200 ns，在氩气吹扫的溶液中的寿命为1100 ns。在相转移条件下，用化学计算量的KF在甲醇/水中处理4a（使用穴状化合物[C 222]），得到的母体化合物4,9-二氨基per醌-3,10-二亚胺几乎定量收率（8） 。用两个摩尔当量的钌配合物[Ru（bpy）_2（丙酮）_2 [（PF_6）_2）处理，原位生成，产生蓝色双核钌配合物[（bpy）_4Ru_2 {mu_2-N，N'： N“，N'”-[{{4,9-（NH_2）_2-3,10-（NH）_2} C_20H_8]}]（PF_6_4（9），通过循环伏安法研究了其氧化还原性质。两个单电子氧化还原步骤（225 mV）的电势差表明金属中心的强耦合，金属中心通过4,9-二氨基亚苄基醌-3,10-二胺桥联配体和对应的配分常数K_c为6.3 X 10〜3。混合价态的UV / Vis吸收光谱在空气中稳定，在930 nm的近红外区域具有特征性的间隔电荷转移（IVCT）带（ lg epsilon = 3.95），据此可以估算出电子耦合参数J为760 cm〜（-1），将化合物9置于R中II类和III类病例的边界肥胖日分类。

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