几种新的反式-双-1-炔基(邻苯二甲酰基萘)硅(VIc-f),-锗(VIIc-f)和-锡(VIIId,f)化合物以及反-双--1--1-炔基(hemiporphyrazinato)的制备描述了锗(XIc,e,f)衍生物。通过在四氢呋喃(THF)中用1-炔基格氏试剂(Vc-f)处理相应的二氯化物(I,II,IV,X; X =(Cl)),以高收率获得产物,并进行光谱表征。被认为是一种新型一维导体的模型。
Synthesis, Structures, and Properties of Crystalline Salts with Radical Anions of Metal-Containing and Metal-Free Phthalocyanines
作者:Dmitri V. Konarev、Alexey V. Kuzmin、Maxim A. Faraonov、Manabu Ishikawa、Salavat S. Khasanov、Yoshiaki Nakano、Akihiro Otsuka、Hideki Yamochi、Gunzi Saito、Rimma N. Lyubovskaya
DOI:10.1002/chem.201404925
日期:2015.1.12
radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal‐free phthalocyanine radical anions [H2Pc(3−)].− (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g‐factors and linewidths that are strongly temperature‐dependent. Salt 11 containing the [NaIPc(2−)]− anions as well
含金属和无金属酞菁的自由基阴离子盐[MPc(3-)] .-,其中M = Cu II,Ni II,H 2,Sn II,Pb II,Ti IV O和V IV O(1 – 10)具有四烷基铵阳离子的单晶体通过芴酮酮基钠的酞菁还原而获得。它们的形成伴随着Pc配体的还原,并影响金属酞菁自由基阴离子的分子结构以及它们的光学和磁性。自由基阴离子的特征在于短的和长C的交替 Ñ亚胺由于芳香族化合物的破坏,它在Pc配体中键合。盐1 – 10在NIR范围内显示833–1041 nm处的新谱带,而Q和Soret谱带则蓝移了0.13–0.25 eV(38–92 nm)和0.04–0.07 eV(4–13 nm)蓝移。 , 分别。具有Ni II,Sn II,Pb II和Ti IV O的自由基阴离子具有S = 1/2自旋态,而[Cu II Pc(3-)] .-和[V IV OPc(3-)] .-含有顺磁性Cu II和V
Coordination Complexes of Pentamethylcyclopentadienyl Iridium(III) Diiodide with Tin(II) Phthalocyanine and Pentamethylcyclopentadienyl Iridium(II) Halide with Fullerene C<sub>60</sub><sup>–</sup> Anions
作者:Dmitri V. Konarev、Sergey I. Troyanov、Alexey V. Kuzmin、Yoshiaki Nakano、Salavat S. Khasanov、Akihiro Otsuka、Hideki Yamochi、Gunzi Saito、Rimma N. Lyubovskaya
DOI:10.1021/om501210s
日期:2015.3.9
Synthetic approaches to iridium complexes of metal phthalocyanines (Pc) and fullerene anions have been developed to give three types of complexes. The compound(Cp*IrIIII2)SnIIPc(2−)}·2C6H4Cl2 (1) (Cp* is pentamethylcyclopentadienyl) is the first crystalline complex of a metal phthalocyanine in which an iridium(III) atom is bonded to the central tin(II) atom of Pc via a Sn–Ir bond length of 2.58 Å
已经开发了金属酞菁(Pc)和富勒烯阴离子的铱配合物的合成方法,可得到三种类型的配合物。化合物(Cp * Ir III I 2)Sn II Pc(2-)}·2C 6 H 4 Cl 2(1)(Cp *为五甲基环戊二烯基)是金属酞菁的第一晶体配合物,其中铱(III) )原子通过2.58Å的Sn–Ir键长度与Pc的中心锡(II)原子键合。In(TBA +)(C 60 •–)(Cp * Ir III I 2)Sn II Pc(2-)}·0.5C 6 H 14(2),(Cp * Ir III I 2)Sn II Pc(2-)}单元与(TBA +)(C 60 •–)共结晶,形成C 60 •阴离子的双链和( Cp * Ir III I 2)Sn II Pc(2-)}。富勒烯和酞菁子系统之间的相互作用是通过Cp * Ir III I 2)Sn II Pc(2-)}的Cp *基团和C 60 •–五边形的π–π堆积来实现的。此外,C
Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States
作者:Dmitri V. Konarev、Alexey V. Kuzmin、Yoshiaki Nakano、Maxim A. Faraonov、Salavat S. Khasanov、Akihiro Otsuka、Hideki Yamochi、Gunzi Saito、Rimma N. Lyubovskaya
DOI:10.1021/acs.inorgchem.5b01906
日期:2016.2.15
6 K was realized between the CpMoI(CO)2 and the [SnIIPc(3−)]•– units in 6 and the π-stacking Fe(CO)4[SnIIPc(3−)]•–}2 dimers of 5, respectively. The [SnIIPc(3−)]•– radical anions substituted the chloride anions in Ph5CpRu(CO)2Cl to form the formally neutral compound Ph5CpRuII(CO)2[SnIIPc(3−)]} (8) in which the negative charge and spin are preserved on [SnIIPc(3−)]•–. The strong antiferromagnetic coupling
锡原子与过渡金属形成稳定的Sn-M键的能力用于制备中性,单阴离子和双阴离子状态的与酞菁锡(II)的过渡金属配合物。这些络合物是通过[Sn IV Cl 2 Pc(3-)] •或[Sn II Pc(3-)] •自由基阴离子与Cp * Mo(CO)2 } 2,CpFe( CO)2 } 2,CpMo(CO)3 } 2,Fe 3(CO)12,Cp * RhCl 2 } 2或Ph 5 CpRu(CO)2Cl。Cp * MoBr(CO)2 [Sn II Pc(2-)]·0.5C 6 H 4 Cl 2(1)和CpFe(CO)2 [Sn II Pc(2-)]·2C 6的中性配位化合物H 4 Cl 2(2)从[Sn IV Cl 2 Pc(3-)] •–中获得。另一方面,过渡金属与[Sn II Pc(3-)] •的配位得到阴离子配位配合物,从而保持了[Sn II Pc(3-)] •上的自旋。。但是,在cryptand
Coordination-induced metal-to-macrocycle charge transfer and effect of cations on reorientation of the CN ligand in the {SnL<sub>2</sub>Mac}<sup>2−</sup> dianions (L = CN<sup>−</sup>, OCN<sup>−</sup>, Im<sup>−</sup>; Mac = phthalo- or naphthalocyanine)
作者:Dmitri V. Konarev、Alexey V. Kuzmin、Alexander F. Shestakov、Salavat S. Khasanov、Rimma N. Lyubovskaya
DOI:10.1039/c9dt00655a
日期:——
obtained. Two anions coordinate to tin(II) atoms in 1–4 to form the SnL2Mac}2− dianions in salts with the general formula crypt[2.2.2](M+)}2SnL2Mac}2− (M = K or Na; Mac: Pc or Nc; L = CN−, OCN−, Im−). The coordination of two ligands to SnII stabilizes these atoms in the higher tin(IV) oxidation state, providing transfer of two electrons from SnII to the macrocycle. The formation of tetraanionic (4−)
Several metallophthalocyanines (MPc: M=Ni(II), Co(II), Zn(II), Pb(II), Fe(II), Sn(II), Cd(II), Mg(II), and Mn(III)) were obtained by heating phthalonitrile with metal salts in alcohols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene. Metal acetylacetonates as well as metal halides were available as metal sources for preparation of metallophthalocyanines by this method.