ISSN:
0044-2313
Keywords:
Phthalocyanines
;
lithium complex
;
crystal structure
;
cyclic voltammetry
;
UV-VIS-NIR spectra
;
vibrational spectra
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Lithiumphthalocyanines: Synthesis, Properties, and Crystal Structure of Bis(triphenylphosphine)iminiumphthalocyaninatolithates with Different Conformations of the CationReaction of tri(n-dodecyl)n-butylammoniumphthalocyaninatolithate, (TDBA)[LiPc2-] with bis(triphenylphosphin)iminiumbromide, (PNP)Br in dichloromethane yields (PNP)[LiPc2-]. It crystallizes in the triclinic space group P1 as dichloromethane solvate (1) and in the monoclinic space group P21/n as hydrate (2). The crystal structures of (1) and (2) are reported. Each salt contains two crystallographically slightly different discrete [LiPc2-]- anions, in which the square-planar coordinated Li+ cation is centered within the planar Pc2- ligand (Dav.(Li—Niso) = 1.945 Å). There are three different conformations for the (PNP) cation: (1) only contains the bent conformer (dav.(P—N) = 1.575 Å; ϕ(P—N—P) = 140.8°), while in (2) an hybrid (dav.(P—N) = 1.562 Å; ϕ(P—N—P) = 158.1°) and the linear conformer (dav.(P—N) = 1.547 Å; ϕ(P—N—P) = 176.8°) are present. The very soluble, blue-green salts melt at 265°C without decomposition. In accordance with cyclovoltammetric data thin films of (PNP)[LiPc2-] are oxidized by NO2 or Br2 to yield brown violet [LiPc-]. The electronic absorption spectra and the vibrational spectra are discussed.
Notes:
Tri(n-dodecyl)n-butylammoniumphthalo-cyaninatolithat, (TDBA)[LiPc2-] bildet mit Bis(triphenylphosphin)iminiumbromid, (PNP)Br in Dichlormethan (PNP)[LiPc2-]. Dieses kristallisiert triklin (RG.:P1) als Dichlormethan-Solvat (1) und monoklin (RG.: P21/n) als Hydrat (2). Nach den Röntgenstrukturanalysen von (1) und (2) enthält jedes Salz zwei kristallographisch unterschiedliche, diskrete [LiPc2-]--Anionen, in denen sich das quadratisch-planar koordinierte Li+-Kation im Zentrum des ebenen Pc2--Liganden befindet (Dgem(Li—Niso) = 1,945 Å). Das (PNP)-Kation tritt in drei verschiedenen Konformationen auf: (1) enthält nur das gewinkelte Konformer (dgem(P—N) = 1,575 Å; ϕ(P—N—P) = 140,8°), (2) dagegen neben dem linearen (dgem(P—N) = 1,547 Å; ω(P—N—P) = 176,8°) ein Hybrid-Konformer (dgem(P—N) = 1,562 Å; ϕ(P—N—P) = 158,1°). Die löslichen, blaugrünen Komplexsalze schmelzen unzersetzt bei 265°C. Dünnfilme von (PNP)[LiPc2-] werden in Übereinstimmung mit cyclovoltammetrischen Daten durch NO2 oder Br2 zu braun-violettem [LiPc-] oxydiert. Die elektronischen Absorptions- und Schwingungsspektren werden diskutiert.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956211017
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